U.S. patent application number 16/323277 was filed with the patent office on 2020-06-18 for method for producing polymeric ring-opening products.
The applicant listed for this patent is COVESTRO DEUTSCHLAND AG. Invention is credited to Christoph GURTLER, Jorg HOFMANN, Jens LANGANKE, Walter LEITNER, Matthias LEVEN, Thomas Ernst MULLER.
Application Number | 20200190261 16/323277 |
Document ID | / |
Family ID | 59564207 |
Filed Date | 2020-06-18 |
United States Patent
Application |
20200190261 |
Kind Code |
A1 |
GURTLER; Christoph ; et
al. |
June 18, 2020 |
METHOD FOR PRODUCING POLYMERIC RING-OPENING PRODUCTS
Abstract
The invention relates to a method for adding a compound (A) to
an H-functional starting compound (BH) in the presence of a
catalyst, wherein the at least one compound (A) is selected from at
least one group consisting of alkylene oxide (A-1), lactone (A-2),
lactide (A-3), cyclic acetal (A-4), lactam (A-5), cyclic anhydride
(A-6) and oxygen-containing heterocyclic compound (A-7) different
from (A-1), (A-2), (A-3), (A-4) and (A-6), wherein the catalyst
comprises an organic, n-protic Bronsted acid (C), wherein
n.gtoreq.2 and is an element of the natural numbers and the degree
of protolysis D is 0<D<n, with n as the maximum number of
transferable protons and D as the calculated proton fraction of the
organic, n-protic Bronsted acid (C). The invention further relates
to an n-protic Bronsted acid (C) having a degree of protolysis D of
0<D<n, wherein n is the maximum number of transferable
protons, with n=2, 3 or 4, and D is the calculated proton fraction
of the organic, n-protic Bronsted acid (C).
Inventors: |
GURTLER; Christoph; (Koln,
DE) ; MULLER; Thomas Ernst; (Aachen, DE) ;
HOFMANN; Jorg; (Krefeld, DE) ; LANGANKE; Jens;
(Mechernich, DE) ; LEVEN; Matthias; (Koln, DE)
; LEITNER; Walter; (Aachen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
COVESTRO DEUTSCHLAND AG |
Leverkusen |
|
DE |
|
|
Family ID: |
59564207 |
Appl. No.: |
16/323277 |
Filed: |
August 9, 2017 |
PCT Filed: |
August 9, 2017 |
PCT NO: |
PCT/EP2017/070140 |
371 Date: |
February 5, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 65/2606 20130101;
C07C 309/35 20130101; C07C 309/29 20130101; C08G 67/04 20130101;
C08G 63/823 20130101; C08G 65/26 20130101; C08G 65/2642 20130101;
C08G 65/2678 20130101; C08G 63/87 20130101 |
International
Class: |
C08G 65/26 20060101
C08G065/26; C08G 63/82 20060101 C08G063/82; C08G 67/04 20060101
C08G067/04; C08G 63/87 20060101 C08G063/87 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 12, 2016 |
EP |
16184028.5 |
Feb 28, 2017 |
EP |
17158356.0 |
Claims
1. A process for addition of a compound (A) onto an H-functional
starter compound (BH) in the presence of a catalyst, wherein the at
least one compound (A) is selected from at least one group
consisting of alkylene oxide (A-1), lactone (A-2), lactide (A-3),
cyclic acetal (A-4), lactam (A-5), cyclic anhydride (A-6) and
oxygen-containing heterocycle compound (A-7) distinct from (A-1),
(A-2), (A-3), (A-4) and (A-6), characterized in that the catalyst
comprises an organic, n-protic Bronsted acid (C), wherein n 2 and
is an element of the natural numbers and the degree of protolysis D
is 0<D<n where n is the maximum number of transferable
protons and D is the calculated proton fraction of the organic,
n-protic Bronsted acid (C) wherein the organic, n-protic Bronsted
acid (C) has a calculated molar mass of .ltoreq.1200 g/mol.
2. The process as claimed in claim 1, wherein the compound (A) is
selected from at least one group consisting of alkylene oxide
(A-1), lactone (A-2), cyclic acetal (A-4) and cyclic anhydride
(A-6).
3. The process as claimed in claim 1, wherein the organic, n-protic
Bronsted acid (C) is a sulfonic acid.
4. The process as claimed in claim 1, wherein the maximum number of
transferable protons n is n=2, 3 or 4.
5. The process as claimed in claim 4, wherein the degree of
protolysis D for diprotic acids where n=2 is 0.2 to 1.9, for
triprotic acids where n=3 is 0.3 to 2.8 and for tetraprotic acids
where n=4 is 0.4 to 3.7.
6. The process as claimed in claim 1, wherein the organic, n-protic
Bronsted acid (C) having the degree of protolysis 0<D<n is
obtained by acid-base reactions with proton transfer by (.alpha.)
addition of suitable amounts of suitable Bronsted bases (E) to the
organic, n-protic Bronsted acids or (.beta.) addition of suitable
amounts of suitable Bronsted acids (E'H) to the salts of the
organic, n-protic Bronsted acids.
7. The process as claimed in claim 6, wherein the organic, n-protic
Bronsted acid (C) having the degree of protolysis 0<D<n is
obtained by acid-base reactions with proton transfer in step
(.alpha.) by addition of Bronsted bases (E) having a pK.sub.b(E) of
.ltoreq.10, preferably having a pK.sub.b(E) of 8 and very
particularly preferably having a pK.sub.b(E) of .ltoreq.5 to the
completely protonated sulfonic acids or (.beta.) by addition of
strong Bronsted acids (E'H) having a pK.sub.s(E'H) of .ltoreq.1 to
the metal salt of a sulfonic acid.
8. The process as claimed in claim 1, wherein the at least one
compound (A) is selected from the group consisting of ethylene
oxide, propylene oxide, styrene oxide, allyl glycidyl ether,
.epsilon.-caprolactone, propiolactone, .beta.-butyrolactone,
.gamma.-butyrolactone, .epsilon.-caprolactam, 1,3-dioxolane,
1,4-dioxane, tetrahydrofuran and 1,3,5-trioxane.
9. The process as claimed in claim 1, wherein the compound (BH) is
one or more compounds and is selected from the group consisting of
mono- or polyvalent alcohols, polyvalent amines, polyvalent thiols,
amino alcohols, thio alcohols, hydroxy esters, polyether polyols,
polyester polyols, polyester ether polyols, polyether carbonate
polyols, polycarbonate polyols, polycarbonates, polyacetals,
polymeric formaldehyde compounds, polyethyleneimines,
polyetheramines, polytetrahydrofurans, polytetrahydrofuranamines,
polyether thiols, polyacrylate polyols, castor oil, the mono- or
diglyceride of ricinoleic acid, monoglycerides of fatty acids,
chemically modified mono-, di- and/or triglycerides of fatty acids
and C1-C24 alkyl fatty acid esters containing on average at least 2
OH groups per molecule.
10. An n-protic Bronsted acid (C) having a degree of protolysis D
of 0<D<n, wherein n is the maximum number of transferable
protons where n=2, 3 or 4 and D is the calculated proton fraction
of the organic, n-protic Bronsted acid (C), characterized in that
the degree of protolysis D for diprotic acids where n=2 is 0.2 to
1.9, for triprotic acids where n=3 is 0.3 to 2.8 and for
tetraprotic acids where n=4 is 0.4 to 3.7, wherein the organic,
n-protic Bronsted acid (C) having the degree of protolysis
0<D<n is obtained by acid-base reactions with proton transfer
by (.beta.) addition of suitable amounts of at least one suitable
Bronsted base (E) to the at least one organic, n-protic Bronsted
acid, wherein the Bronsted base (E) contains at least one cation
(F) selected from the group consisting of alkali metal-containing,
alkaline earth metal-containing, metalloid-containing, transition
metal-containing, lanthanoid metal-containing, aliphatic
ammonium-containing and phosphonium-containing and
sulfonium-containing cations or (.chi.) addition of suitable
amounts of at least one suitable Bronsted acid (E'H) to the salt of
the at least one organic, n-protic Bronsted acid, wherein the salts
of the organic, n-protic Bronsted acid contains at least one cation
(F') selected from the group consisting of alkali metal-containing,
alkaline earth metal-containing, metalloid-containing, transition
metal-containing, lanthanoid metal-containing, aliphatic
ammonium-containing and phosphonium-containing and
sulfonium-containing cations, wherein the n-protic Bronsted acid
(C) is at least one sulfonic acid and wherein the at least one
sulfonic acid is selected from the group consisting of
1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid and
1,3-benzenedisulfonic acid, preferably 1,5-naphthalenedisulfonic
acid, 2,6-naphthalenedisulfonic acid, and very particularly
preferably 2,6-naphthalenedisulfonic acid.
11. The n-protic Bronsted acid (C) as claimed in claim 10, wherein
the cation (F) is selected from the group consisting of lithium
cation, sodium cation, potassium cation, rubidium cation, cesium
cation, magnesium cation, calcium cation, strontium cation, barium
cation, scandium cation, titanium cation, zinc cation, aluminum
cation, aliphatic primary ammonium ions, aliphatic secondary
ammonium ions, aliphatic tertiary ammonium ions, aliphatic
quaternary ammonium ions, phosphonium ions, sulfonium ions and
sulfoxonium ions, preferably from lithium cation, sodium cation,
potassium cation, magnesium cation, calcium cation, quaternary
ammonium ions and triphenylphosphonium ions and particularly
preferably from sodium cation, potassium cation, magnesium cation
and n-butylammonium ion.
12. The n-protic Bronsted acid (C) as claimed in claim 10, wherein
the cation (F') is selected from the group consisting of lithium
cation, sodium cation, potassium cation, rubidium cation, cesium
cation, magnesium cation, calcium cation, strontium cation, barium
cation, scandium cation, titanium cation, zinc cation, aluminum
cation, aliphatic primary ammonium ions, aliphatic secondary
ammonium ions, aliphatic tertiary ammonium ions, aliphatic
quaternary ammonium ions, phosphonium ions, sulfonium ions and
sulfoxonium ions, preferably from lithium cation, sodium cation,
potassium cation, magnesium cation, calcium cation, quaternary
ammonium ions and triphenylphosphonium ions and particularly
preferably from sodium cation, potassium cation, magnesium cation
and n-butylammonium ion.
13. The n-protic Bronsted acid (C) as claimed in claim 10, wherein
the at least one Bronsted base (E) is selected from the group
consisting of lithium hydroxide, sodium hydroxide, potassium
hydroxide, rubidium hydroxide, cesium hydroxide, magnesium
hydroxide, calcium hydroxide, strontium hydroxide, barium
hydroxide, scandium hydroxide, titanium hydroxide, zinc hydroxide,
aluminum hydroxide, aliphatic primary ammonium hydroxides,
aliphatic secondary ammonium hydroxides, aliphatic tertiary
ammonium hydroxides, aliphatic quaternary ammonium hydroxides,
phosphonium hydroxides, aliphatic primary ammonium alkoxides,
aliphatic secondary ammonium alkoxides, aliphatic tertiary ammonium
alkoxides, aliphatic quaternary ammonium alkoxides, phosphonium
alkoxides, butylithium, potassium tert-butoxide,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), primary aliphatic amines,
secondary aliphatic amines, tertiary aliphatic amines, primary
cycloaliphatic amines, secondary cycloaliphatic amines, tertiary
cycloaliphatic amines and phosphonium alkoxides, preferably from
sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium
hydroxide, calcium hydroxide, aliphatic quaternary ammonium
alkoxides, phosphonium alkoxides, ammonia, triethylamine,
trimethylamine, diethylamine, propylamine, methylamine,
dimethylamine, ethylamine, ethylenediamine, 1,3-diaminopropanes,
putrescine, 1,5-diaminopentane, hexamethylenediamine,
1,2-diaminopropanes, diaminocyclohexane, n-propylamine,
di-n-propylamine, tri-n-propylamin, isopropylamine,
diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine,
diisobutylamine, 2-aminobutane, 2-ethylhexylamine,
di-2-ethylhexylamine, cyclohexylamine, dicyclohexylamine,
dimethylaminopropylamine, triethylenediamine,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), particularly preferably
from sodium hydroxide, potassium hydroxide, lithium hydroxide,
magnesium hydroxide, tetra(n-butyl)ammonium methoxide,
tetra(n-butyl)ammonium ethoxide and tetra(n-butyl)ammonium
isopropoxide.
14. The n-protic Bronsted acid (C) as claimed in claim 10, wherein
the at least one Bronsted acid (E'H) is selected from the group
consisting of aliphatic fluorinated sulfonic acids, aromatic
fluorinated sulfonic acids, trifluoromethanesulfonic acid,
perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic
acid, fluorosulfonic acid, bis(trifluoromethane)sulfonimide,
hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid,
sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic
acid, paratoluenesulfonic acid, aromatic sulfonic acids and
aliphatic sulfonic acids, preferably from trifluoromethanesulfonic
acid, perchloric acid, hydrochloric acid, hydrobromic acid,
hydroiodic acid, fluorosulfonic acid,
bis(trifluoromethane)sulfonimide, hexafluorantimonic acid,
pentacyanocyclopentadiene, picric acid, sulfuric acid, nitric acid,
trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic
acid, methanesulfonic acid and paratoluenesulfonic acid,
particularly preferably from trifluoromethanesulfonic acid,
perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic
acid, bis(trifluoromethane)sulfonimide, pentacyanocyclopentadiene,
sulfuric acid, nitric acid and trifluoroacetic acid.
15. (canceled)
16. Sulfonic acid as claimed in claim 10, wherein the degree of
protolysis D is 0.8 to 1.8, preferably 1.1 to 1.7.
Description
[0001] The present invention relates to a process for addition of a
compound (A) onto an H-functional starter compound (BH) in the
presence of a catalyst, wherein the at least one compound (A) is
selected from at least one group consisting of alkylene oxide
(A-1), lactone (A-2), lactide (A-3), cyclic acetal (A-4), lactam
(A-5), cyclic anhydride (A-6) and oxygen-containing heterocyclic
compound (A-7) distinct from (A-1), (A-2), (A-3), (A-4) and (A-6),
wherein the catalyst comprises an organic, n-protic Bronsted acid
(C), wherein n.gtoreq.2 and is an element of the natural numbers
and the degree of protolysis D is 0<D<n where n is the
maximum number of transferable protons and D is the calculated
proton fraction of the organic, n-protic Bronsted acid (C). The
invention further relates to an n-protic Bronsted acid (C) having a
degree of protolysis D of 0<D<n, wherein n is the maximum
number of transferable protons where n=2, 3 or 4 and D is the
calculated proton fraction of the organic, n-protic Bronsted acid
(C).
[0002] The present invention further relates to polymeric
ring-opening products obtainable by the process according to the
invention, for example polyols and also polyurethane polymers
producible therefrom.
[0003] The present invention thirdly relates to n-protic Bronsted
acids (C) having a degree of protolysis D of 0<D<n, wherein n
is the maximum number of transferable protons where n=2, 3 or 4 and
D is the calculated proton fraction of the organic, n-protic
Bronsted acid (C), wherein the degree of protolysis D for diprotic
acids where n=2 is 0.2 to 1.9, for triprotic acids where n=3 is 0.3
to 2.8 and for tetraprotic acids where n=4 is 0.4 to 3.7.
[0004] At the present time, more than 11 million tonnes of
polyurethane per annum are produced globally. From the aspect of a
more sustainable manner of production, the use of polyols
originating at least partly from renewable raw material sources is
desirable as polyurethane raw materials. Suitable C.sub.1-building
blocks include in particular CO.sub.2 and formaldehyde (J. Langanke
et al., Green Chem., 2014, 16, 1865-1870 and J. Polym. Sci. A:
Polym. Chem., 2015, 53, 2071-2074). These are not tied to the
availability of crude oil and are also inexpensive.
[0005] Formaldehyde is polymerizable into polyoxymethylene (POM).
When polymeric polyols are used as starters this affords
polyoxymethylene copolymers. Sources of formaldehyde generally
include gaseous formaldehyde (monomer), paraformaldehyde (polymer)
and trioxane (trimer). The reaction conditions of polymerization
also have a great influence on the structure of the thus obtained
block copolymers: the anionic polymerization of gaseous
formaldehyde in the presence of a for example difunctional starter
polyol results in a triblock structure in which the starter polyol
bears two POM chains which form the terminus of the block
copolymer. From the aspect of chemical stability it is advantageous
when the terminal OH group of a polyoxymethylene unit is
derivatized in the polymer. This prevents the stepwise degradation
of the POM chain.
[0006] The cationic polymerization of alkylene oxides such as for
example propylene oxide, ethylene oxide onto hydroxyl groups in the
presence of Lewis acids or Bronsted superacids such as for example
HBH.sub.4, HSbF.sub.4, HPF.sub.4, CF.sub.3SO.sub.3H and HClO.sub.4
is described in "Chemistry of Polyols for Polyurethanes" by M.
Ionescu in the section "Polyetherpolyols by Cationic Polymerisation
Process" on page 245-246. The polymerization rate of alkylene
oxides onto H-functional starter compounds and especially of
propylene oxides is markedly higher than in the anionic
polymerization even at low temperatures but undesired side
reactions such as the formation of cyclic byproducts, such as for
example dioxanes and crown ethers, result. Accordingly,
acid-catalyzed cationic polymerization is unsuitable for industrial
production of polyether polyols on account of the formation of the
high proportion of 15-25% of cyclic oligomers.
[0007] The use of borate esters in conjunction with halides as a
catalyst in the ethoxylation of base-sensitive alcohols is
described in the publication by K. G. Moloy, Adv. Synth. Catal.,
2010, 352, 821-826. However, only low molecular weight alcohols are
ethoxylated as starter compounds and a high catalyst proportion and
lengthy reaction times are necessary. In addition boric acid and
esters thereof are regarded as teratogenic and mutagenic.
[0008] US 2012/0259090 A1 discloses a catalytic process for
copolymerization of ethylene oxide and tetrahydrofuran, wherein a
high proportion of byproducts such as oligomeric cyclic ethers are
formed. The employed catalyst consists of a polymeric
perfluorinated sulfonic acid produced by copolymerization of
tetrafluoroethylene and
CF2=CF--O--CF2CF(CF.sub.3)--O--CF.sub.2CF.sub.2SO.sub.2F and
subsequent hydrolysis. Conditioning of the polymeric catalyst
involves a treatment with water and ethylene oxide and subsequent
drying over a period of nearly 45 hours. Moreover, only partial
conversion of the ethylene oxide and tetrahydrofuran into the
corresponding copolymer results despite a comparatively high
catalyst loading. Byproducts are also formed.
[0009] U.S. Pat. No. 4,120,903 describes a process for
acid-catalyzed polymerization of tetrahydrofuran, wherein a
commercial polymer having the trade name Nafion.RTM. is employed as
catalyst. The Nation.RTM. catalysts are obtained with equivalent
masses of 943 to 1500 by copolymerization of tetrafluoroethylene or
hexafluoropropylene with perfluorinated sulfonic acid ethers. This
corresponds to calculated molar masses of the resulting copolymers
of 420682 g/mol bis 2910435 g/mol. However only a partial
conversion of 55.6% results despite a high catalyst loading and a
long reaction time of 65 h. After removal of the unreacted
tetrahydrofuran the polytetrahydrofuran is in a second reaction
step stabilized by addition of 1,4-butanediol.
[0010] Furthermore, as a strongly acidic, polymeric catalyst
Nafion.RTM. is known to catalyze rearrangements of alkylene oxides,
wherein epoxides isomerize into the corresponding aldehydes and
ketones under reaction conditions as described in Industrial &
Engineering Chemistry Research, 2005, 44(23), 8468-8498.
[0011] WO2015155094 (A1) describes a process for producing
polyoxymethylene block copolymers comprising the step of activating
the DMC catalyst in the presence of an OH-terminated polymeric
formaldehyde starter compound with a defined amount of alkylene
oxide and an optional subsequent polymerization with alkylene
oxides and optionally further co-comonomers. The OH-terminated
polymeric formaldehyde starter compound is reacted with alkylene
oxides at the mildest possible temperatures during the activation
phase to avoid a depolymerization of the thermally
labile/metastable H-functional starter compound. The thus obtained
polyoxymethylene block copolymers are thermally and chemically
stable.
[0012] WO 2004/096746 A1 and US 2006/0205915 A1 disclose the
reaction of formaldehyde oligomers with alkylene oxides and/or
isocyanates. In this method the described use of formaldehyde
oligomers HO--(CH.sub.2O).sub.n--H affords polyoxymethylene block
copolymers having a relatively narrow molar mass distribution of
n=2-19, an additional thermal removal process step being required
for the provision of the formaldehyde oligomers from aqueous
formalin solution. The obtained formaldehyde oligomer solutions are
not storage-stable and therefore require immediate subsequent
further processing.
[0013] The prior art does not describe a satisfactory method for
chain extension of chemically/thermally labile H-functional starter
compounds, for example polycarbonate polyols or polyacetal
compounds (e.g. poly/para-formaldehyde) with alkylene oxide
compounds, since known catalyst systems often catalyze the
homopolymerization as a secondary reaction. Furthermore,
cationically catalyzed additions of alkylene oxides onto
H-functional starter compounds in the presence of Bronsted acids
result in a higher proportion of undesired oligomeric
byproducts.
[0014] The present application had for its object to provide
improved, non-polymeric catalyst systems having sufficient
reactivity which reduce the disadvantages described in the prior
art in order thus to realize a more selective reaction of
preferably thermally labile H-functional starter compounds with
correspondingly reactive compounds, especially alkylene oxides,
under the mildest possible reaction conditions to afford
chain-extended addition products, especially to afford
chain-extended polyols, and to reduce the proportion of undesired
cyclic byproducts and degradation products and/or the formation of
isomerization products such as for example of aldehydes or ketones
and their possible descendent products. It is moreover desirable
for the catalysts used to be free from heavy metals and for their
precursors to be commercially available or for the catalysts thus
to be rapidly and easily synthesized and conditioned.
[0015] The object is achieved according to the invention by a
process for addition of a compound (A) onto an H-functional starter
compound (BH) in the presence of a catalyst, wherein the at least
one compound (A) is selected from at least one group consisting of
alkylene oxide (A-1), lactone (A-2), lactide (A-3), cyclic acetal
(A-4), lactam (A-5), cyclic anhydride (A-6) and oxygen-containing
heterocyclic compound (A-7) distinct from (A-1), (A-2), (A-3),
(A-4) and (A-6), characterized in that the catalyst comprises an
organic, n-protic Bronsted acid (C), wherein n.gtoreq.2 and is an
element of the natural numbers and the degree of protolysis D is
0<D<n where n is the maximum number of transferable protons
and D is the calculated proton fraction of the organic, n-protic
Bronsted acid (C).
[0016] In one embodiment of the process according to the invention,
the addition of the compound (A) onto the H-functional starter
compound (BH) in the presence of the catalyst preferably affords a
ring-opening product, preferably a polymeric ring-opening product,
wherein this is to be understood as meaning the optionally
catalytically induced ring opening of the compound (A) in the
course of the addition onto the H-functional starter compound (BH)
and/or onto ring-opening products of the compound (A) that have
previously undergone addition reaction.
[0017] One embodiment of the process according to the invention
comprises the addition of the compound (A) onto the H-functional
starter compound (BH) in the presence of a catalyst, wherein the at
least one compound (A) is selected from at least one group
consisting of alkylene oxide (A-1), lactone (A-2), lactide (A-3),
cyclic acetal (A-4), lactam (A-5) and cyclic anhydride (A-6),
wherein the catalyst comprises an organic, n-protic Bronsted acid
(C), wherein n.gtoreq.2 and is an element of the natural numbers
and the degree of protolysis D is 0<D<n where n is the
maximum number of transferable protons and D is the calculated
proton fraction of the organic, n-protic Bronsted acid (C).
[0018] A preferred embodiment of the process according to the
invention comprises the addition of the compound (A) onto the
H-functional starter compound (BH) in the presence of the catalyst,
wherein the at least one compound (A) is selected from at least one
group consisting of alkylene oxide (A-1), lactone (A-2), cyclic
acetal (A-4) and cyclic anhydride (A-6), characterized in that the
catalyst comprises an organic, n-protic Bronsted acid (C), wherein
n.gtoreq.2 and is an element of the natural numbers and the degree
of protolysis D is 0<D<n where n is the maximum number of
transferable protons and D is the calculated proton fraction of the
organic, n-protic Bronsted acid (C).
[0019] An alternative embodiment of the process according to the
invention comprises the addition of the compound (A) onto the
H-functional starter compound (BH) in the presence of a catalyst,
wherein the at least one compound (A) is selected from at least one
group consisting of alkylene oxide (A-1) and oxygen-containing
heterocyclic compound (A-7) distinct from (A-1), (A-2), (A-3),
(A-4) and (A-6), wherein the catalyst comprises an organic,
n-protic Bronsted acid (C), wherein n.gtoreq.2 and is an element of
the natural numbers and the degree of protolysis D is 0<D<n
where n is the maximum number of transferable protons and D is the
calculated proton fraction of the organic, n-protic Bronsted acid
(C).
Compound (A)
[0020] When compound (A) is an alkylene oxide (A-1) this may be for
example an epoxide having 2-45 carbon atoms. In a preferred
embodiment of the process the alkylene oxide (A-1) is selected from
at least one compound from the group consisting of ethylene oxide,
propylene oxide, 1-butene oxide, 2,3-butene oxide,
2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide,
2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene
oxide, epoxides of C6-C22 .alpha.-olefins, such as 1-hexene oxide,
2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide,
4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene
oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene
oxide, 1-dodecene oxide, 4-methyl-1,2-pentene oxide, cyclopentene
oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide,
styrene oxide, methylstyrene oxide, pinene oxide, allyl glycedyl
ether, vinylcyclohexene oxide, cyclooctadiene monoepoxide,
cyclododecatriene monoepoxid, butadiene monoepoxide, isoprene
monoepoxide, limonene oxide, 1,4-divinylbenzene monoepoxide,
1,3-divinylbenzene monoepoxide, glycidyl acrylate and
glycidylmethacrylate, mono- or polyepoxidized fats as mono-, di-
and triglycerides, epoxidized fatty acids, C1-C24 esters of
epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives
of glycidol, for example glycidyl ethers of C1-C22 alkanols and
glycidyl esters of C1-C22 alkanecarboxylic acids. Examples of
derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl
ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl
glycidyl ether.
[0021] In a particularly preferred embodiment of the process the
alkylene oxide (A-1) is selected from at least one compound from
the group consisting of ethylene oxide, propylene oxide, styrene
oxide and allyl glycidyl ether are used.
[0022] In a preferred embodiment of the process the lactone (A-2)
is selected from at least one compound from the group consisting of
4-membered-ring lactones such as propiolactone,
.beta.-butyrolactone, .beta.-isovalerolactone, .beta.-caprolactone,
.beta.-isocaprolactone, .beta.-methyl-.beta.-valerolactone,
5-membered-ring lactones, such as .gamma.-butyrolactone,
.gamma.-valerolactone, 5-methylfuran-2(3H)-one,
5-methylidenedihydrofuran-2(3H)-one, 5-hydroxyfuran-2(5H)-one,
2-benzofuran-1(3H)-one and 6-methyl-2-benzofuran-1(3H)-one,
6-membered-ring lactones, such as .delta.-valerolactone,
1,4-dioxan-2-one, dihydrocoumarin, 1H-isochromen-1-one,
8H-pyrano[3,4-b]pyridin-8-one, 1,4-dihydro-3H-isochromen-3-one,
7,8-dihydro-5H-pyrano[4,3-b]pyridin-5-one,
4-methyl-3,4-dihydro-1H-pyrano[3,4-b]pyridin-1-one,
6-hydroxy-3,4-dihydro-1H-isochromen-1-one,
7-hydroxy-3,4-dihydro-2H-chromen-2-one,
3-ethyl-1H-isochromen-1-one, 3-(hydroxymethyl)-1H-isochromen-1-one,
9-hydroxy-1H,3H-benzo[de]isochromen-1-one,
6,7-dimethoxy-1,4-dihydro-3H-isochromen-3-one and
3-phenyl-3,4-dihydro-1H-isochromen-1-one, 7-membered-ring lactones,
such as .epsilon.-caprolactone, 1,5-dioxepan-2-one,
5-methyloxepan-2-one, oxepane-2,7-dione, thiepan-2-one,
5-chlorooxepan-2-one, (4S)-4-(propan-2-yl)oxepan-2-one,
7-butyloxepan-2-one, 5-(4-aminobutyl)oxepan-2-one,
5-phenyloxepan-2-one, 7-hexyloxepan-2-one,
(5S,7S)-5-methyl-7-(propan-2-yl)oxepan-2-one,
4-methyl-7-(propan-2-yl)oxepan-2-one, and lactones with higher
numbers of ring members, such as
(7E)-oxacycloheptadec-7-en-2-one.
[0023] In a particularly preferred embodiment of the process the
lactone (A-2) is selected from at least one compound from the group
consisting of .epsilon.-caprolactone, propiolactone,
.beta.-butyrolactone and .gamma.-butyrolactone.
[0024] In a preferred embodiment of the process the lactide (A-3)
is selected from at least one compound from the group consisting of
glycolide (1,4-dioxane-2,5-dione), L-lactide
(L-3,6-dimethyl-1,4-dioxane-2,5-dione), D-lactide, DL-lactide,
mesolactide and 3-methyl-1,4-dioxane-2,5-dione,
3-hexyl-6-methyl-1,4-dioxane-2,5-diones, and
3,6-di(but-3-en-1-yl)-1,4-dioxane-2,5-dione (in each case inclusive
of optically active forms).
[0025] In a preferred embodiment of the process the lactide (A-3)
is selected from at least one compound from the group consisting of
L-lactide.
[0026] In a preferred embodiment of the process the cyclic acetal
(A-4) is selected from at least one compound from the group
consisting of 1,3,5-trioxane, 1,3-dioxane and 1,3-dioxolane.
[0027] In a preferred embodiment of the process the lactam (A-5) is
selected from at least one compound from the group consisting of
.beta.-, .gamma.-, .delta.- or .epsilon.-lactams.
[0028] When the compound (A) is a cyclic anhydride (A-6) this may
contain for example 2 to 36, preferably 2 to 12, carbon atoms. In a
preferred embodiment of the process the cyclic anhydride (A-6) is
selected from at least one compound from the group consisting of
4-cyclohexene-1,2-dioic anhydride, 4-methyl-4-cyclohexene-1,2-dioic
anhydride, 5,6-norbornene-2,3-dioic anhydride,
allyl-5,6-norbornene-2,3-dioic anhydride, dodecenylsuccinic
anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic
anhydride, octadecenylsuccinic anhydride, succinic anhydride,
maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic
anhydride, diphenic anhydride, tetrahydrophthalic anhydride,
methyltetrahydrophthalic anhydride, norbornenedioic anhydride and
chlorination products thereof, succinic anhydride, glutaric
anhydride, diglycolic anhydride, 1,8-naphthalic anhydride, succinic
anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic
anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic
anhydride, 3- and 4-nitrophthalic anhydride, tetrachlorophthalic
anhydride, tetrabromophthalic anhydride, itaconic anhydride,
dimethylmaleic anhydride, allylnorbornenedioic anhydride,
3-methylfuran-2,5-dione, 3-methyldihydrofuran-2,5-dione,
dihydro-2H-pyran-2,6(3H)-dione, 1,4-dioxane-2,6-dione,
2H-pyran-2,4,6(3H,5H)-trione, 3-ethyldihydrofuran-2,5-dione,
3-methoxydihydrofuran-2,5-dione,
3-(prop-2-en-1-yl)dihydrofuran-2,5-dione,
N-(2,5-dioxotetrahydrofuran-3-yl)formamide and
3[(2E)-but-2-en-1-yl]dihydrofuran-2,5-dione.
[0029] In a particularly preferred embodiment of the process the
cyclic polycarboxylic anhydride (A-6) is selected from at least one
compound from the group consisting of succinic anhydride, maleic
anhydride, itaconic anhydride and phthalic anhydride.
[0030] When the compound (A) is an oxygen-containing heterocyclic
compound (A-7) distinct from (A-1), (A-2), (A-3), (A-4) and (A-6)
this may contain for example 3 to 36, preferably 3 to 12, carbon
atoms in the ring.
[0031] In a preferred embodiment of the process the
oxygen-containing heterocyclic compound (A-7) distinct from (A-1),
(A-2), (A-3), (A-4) and (A-6) is selected from at least one
compound of the group consisting of unsubstituted or substituted
oxetanes, unsubstituted or substituted oxolanes, unsubstituted or
substituted oxanes and unsubstituted or substituted oxepanes.
[0032] In a particularly preferred embodiment of the process the
oxygen-containing heterocyclic compound (A-7) distinct from (A-1),
(A-2), (A-3), (A-4) and (A-6) is selected from at least one
compound from the group consisting of trimethylene oxide, furan,
tetrahydrofuran, tetrahydropyran, oxacycloheptatriene and
hexamethylene oxide.
[0033] In a further preferred embodiment of the process according
to the invention the at least one compound (A) is selected from the
group consisting of ethylene oxide, propylene oxide, styrene oxide,
allyl glycidyl ether, .epsilon.-caprolactone, propiolactone,
.beta.-butyrolactone, .gamma.-butyrolactone, .epsilon.-caprolactam,
1,3-dioxolane, 1,4-dioxane, tetrahydrofuran and 1,3,5-trioxane. In
a particularly preferred embodiment the at least one compound (A)
is selected from the group consisting of ethylene oxide, propylene
oxide and .beta.butyrolactone.
[0034] In a further preferred embodiment of the process according
to the invention the at least one compound (A) is selected from the
group consisting of ethylene oxide, propylene oxide, styrene oxide,
allyl glycidyl ether, .epsilon.-caprolactone, propiolactone,
.beta.-butyrolactone, .gamma.-butyrolactone, .epsilon.-caprolactam,
1,3-dioxolane and 1,3,5-trioxane. In a particularly preferred
embodiment the at least one compound (A) is selected from the group
consisting of ethylene oxide, propylene oxide and
-butyrolactone.
[0035] In a further alternatively preferred embodiment of the
process according to the invention the at least one compound (A) is
selected from the group consisting of ethylene oxide, propylene
oxide and tetrahydrofuran.
Compound (BH)
[0036] Employable as suitable H-functional starter compounds (BH),
also known as starters, are compounds having alkoxylation-active H
atoms. Alkoxylation-active groups having active H atoms include,
for example, --OH, --NH.sub.2 (primary amines), --NH-- (secondary
amines), --SH, and --CO.sub.2H, preference being given to --OH and
--NH.sub.2, particular preference being given to --OH. As
H-functional starter compound one or more compounds may for example
be selected from the group comprising mono- or polyvalent alcohols,
polyvalent amines, polyvalent thiols, amino alcohols, thio
alcohols, hydroxy esters, polyether polyols, polyester polyols,
polyester ether polyols, polyether carbonate polyols, polycarbonate
polyols, polycarbonates, polyacetals, polymeric formaldehyde
compounds, polyethyleneimines, polyetheramines (for example the
products called Jeffamines.RTM. from Huntsman, for example D-230,
D-400, D-2000, T-403, T-3000, T-5000 or corresponding BASF
products, for example Polyetheramine D230, D400, D200, T403,
T5000), polytetrahydrofurans (e.g. PolyTHF.RTM. from BASF, for
example PolyTHF.RTM. 250, 650S, 1000, 10005, 1400, 1800, 2000),
polytetrahydrofuranamines (BASF product Polytetrahydrofuranamine
1700), polyether thiols, polyacrylate polyols, castor oil, the
mono- or diglyceride of ricinoleic acid, monoglycerides of fatty
acids, chemically modified mono-, di- and/or triglycerides of fatty
acids, and C1-C24 alkyl fatty acid esters containing an average of
at least 2 OH groups per molecule. The C1-C23 alkyl fatty acid
esters which contain on average at least 2 OH groups per molecule
are, for example, commercial products such as Lupranol Balance.RTM.
(BASF AG), Merginol.RTM. products (Hobum Oleochemicals GmbH),
Sovermol.RTM. products (Cognis Deutschland GmbH & Co. KG), and
Soyol.RTM..TM. products (USSC Co.).
[0037] In a preferred embodiment of the process according to the
invention the compound (BH) is selected from the group consisting
of polyether polyol, polyether carbonate polyol and polycarbonate
polyol. Production of the polyether carbonate polyol and of the
polycarbonate polyol is carried out by catalytic addition of carbon
dioxide and alkylene oxides onto a further H-functional starter
compound. Production of the polyether carbonate polyol and of the
polycarbonate polyol is preferably carried out by catalytic
addition of carbon dioxide and ethylene oxide and/or propylene
oxide onto a further H-functional starter compound. Employable
monofunctional starter compounds include alcohols, amines, thiols
and carboxylic acids. Employable monofunctional alcohols include:
methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,
tert-butanol, 3-buten-1-ol, 3-Butyn-1-ol, 2-methyl-3-buten-2-ol, 2
methyl-3-Butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol,
1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol,
1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol,
3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol,
2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl,
2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine. Suitable
monofunctional amines include: butylamine, tert-butylamine,
pentylamine, hexylamine, aniline, aziridine, pyrrolidine,
piperidine, morpholine. Employable monofunctional thiols include:
ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol,
3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol. Examples of
monofunctional carboxylic acids include: formic acid, acetic acid,
propionic acid, butyric acid, fatty acids such as stearic acid,
palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic
acid, acrylic acid.
[0038] Polyvalent alcohols suitable as H-functional starter
compounds include for example divalent alcohols (such as, for
example, ethylene glycol, diethylene glycol, propylene glycol,
dipropylene glycol, 1,3-propanediol, 1,4-butanediol,
1,4-butenediol, 1,4-butynediol, neopentyl glycol,
1,5-pentantanediol, methylpentanediols (such as, for example,
3-methyl-1,5-pentanediol), 1,6-hexanediol; 1,8-octanediol,
1,10-decanediol, 1,12-dodecanediol, bis(hydroxymethyl)cyclohexanes
(such as, for example, 1,4-bis(hydroxymethyl)cyclohexane),
triethylene glycol, tetraethylene glycol, polyethylene glycols,
dipropylene glycol, tripropylene glycol, polypropylene glycols,
dibutylene glycol, and polybutylene glycols); trivalent alcohols
(such as, for example, trimethylolpropane, glycerol,
trishydroxyethyl isocyanurate, castor oil); tetravalent alcohols
(such as, for example, pentaerythritol); polyalcohols (such as, for
example, sorbitol, hexitol, sucrose, starch, starch hydrolyzates,
cellulose, cellulose hydrolyzates, hydroxy-functionalized fats and
oils, especially castor oil), and also all products of modification
of these aforementioned alcohols with different amounts of
.epsilon.-caprolactone.
[0039] The H-functional starter compounds may also be selected from
the substance class of the polyether polyols, in particular those
having a molecular weight M.sub.n in the range from 100 to 4000
g/mol. Preference is given to polyether polyols made up of
repeating ethylene oxide and propylene oxide units, preferably
having a proportion of 35% to 100% of propylene oxide units,
particularly preferably having a proportion of 50% to 100% of
propylene oxide units. These may be random copolymers, gradient
copolymers, alternating copolymers or block copolymers of ethylene
oxide and propylene oxide. Suitable polyether polyols constructed
from repeating propylene oxide and/or ethylene oxide units are, for
example, the Desmophen.RTM., Acclaim.RTM., Arcol.RTM.,
Baycoll.RTM., Bayfill.RTM., Bayflex.RTM., Baygal.RTM., PET.RTM. and
polyether polyols from Covestro AG (for example Desmophen.RTM.
3600Z, Desmophen.RTM. 1900U, Acclaim.RTM. Polyol 2200, Acclaim.RTM.
Polyol 40001, Arcol.RTM. Polyol 1004, Arcol.RTM. Polyol 1010,
Arcol.RTM. Polyol 1030, Arcol.RTM. Polyol 1070, Baycoll.RTM. BD
1110, Bayfill.RTM. VPPU 0789, Baygal.RTM. K55, PET.RTM. 1004,
Polyether.RTM. S180). Further suitable homopolyethylene oxides are,
for example, the Pluriol.RTM. E products from BASF SE, suitable
homopolypropylene oxides are, for example, the Pluriol.RTM. P
products from BASF SE, and suitable mixed copolymers of ethylene
oxide and propylene oxide are, for example, the Pluronic.RTM. PE or
Pluriol.RTM. RPE products from BASF SE.
[0040] The H-functional starter compounds may also be selected from
the substance class of the polyester polyols, in particular those
having a molecular weight M.sub.n in the range from 200 to 4500
g/mol. Polyesters having a functionality of at least two may be
used as the polyester polyols. It is preferable when polyester
polyols consist of alternating acid and alcohol units. Employable
acid components include for example succinic acid, maleic acid,
maleic anhydride, adipic acid, phthalic anhydride, phthalic acid,
isophthalic acid, terephthalic acid, tetrahydrophthalic acid,
tetrahydrophthalic anhydride, hexahydrophthalic anhydride or
mixtures of the recited acids and/or anhydrides. Alcohol components
employed include for example ethanediol, 1,2-propanediol,
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol,
1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, diethylene
glycol, dipropylene glycol, trimethylolpropane, glycerol,
pentaerythritol or mixtures of the stated alcohols. Employing
divalent or polyvalent polyether polyols as the alcohol component
affords polyester ether polyols which can likewise serve as starter
compounds for producing the polyether carbonate polyols. It is
preferable to use polyether polyols where M.sub.n=150 to 2000 g/mol
for producing the polyester ether polyols. H-functional starter
compounds that may be employed further include polycarbonate diols,
in particular those having a molecular weight M.sub.n in the range
from 150 to 4500 g/mol, preferably 500 to 2500 g/mol, prepared, for
example, by reaction of phosgene, dimethyl carbonate, diethyl
carbonate or diphenyl carbonate with difunctional alcohols or
polyester polyols or polyether polyols. Examples relating to
polycarbonates may be found for example in EP-A 1359177. Employable
polycarbonate diols include for example the Desmophen.RTM.
C-products from CovestroAG, for example Desmophen.RTM. C 1100 or
Desmophen.RTM. C 2200.
[0041] A further embodiment of the invention may employ polyether
carbonate polyols (for example Cardyon.RTM. polyols from Covestro),
polycarbonate polyols (for example Converge.RTM. polyols from
Novomer/Saudi Aramco, NEOSPOL polyols from Repsol etc.) and/or
polyether ester carbonate polyols as H-functional starter
compounds. Polyether carbonate polyols, polycarbonate polyols
and/or polyether ester carbonate polyols may in particular be
obtained by reaction of alkylene oxides, preferably ethylene oxide,
propylene oxide or mixtures thereof, optionally further comonomers,
with CO.sub.2 in the presence of a further H-functional starter
compound and using catalysts. These catalysts include double metal
cyanide catalysts (DMC catalysts) and/or metal complex catalysts
for example based on the metals zinc and/or cobalt, for example
zinc glutarate catalysts (described for example in M. H. Chisholm
et al., Macromolecules 2002, 35, 6494), so-called zinc diiminate
catalysts (described for example in S. D. Allen, J. Am. Chem. Soc.
2002, 124, 14284) and so-called cobalt salen catalysts (described
for example in U.S. Pat. No. 7,304,172 B2, US 2012/0165549 A1)
and/or manganese salen complexes. An overview of the known
catalysts for the copolymerization of alkylene oxides and CO.sub.2
is provided for example in Chemical Communications 47 (2011)
141-163. The use of different catalyst systems, reaction conditions
and/or reaction sequences results in the formation of random,
alternating, block-type or gradient-type polyether carbonate
polyols, polycarbonate polyols and/or polyether ester carbonate
polyols. To this end, these polyether carbonate polyols,
polycarbonate polyols and/or polyether ester carbonate polyols used
as H-functional starter compounds may be produced beforehand in a
separate reaction step.
[0042] The H-functional starter compounds generally have an OH
functionality (i.e., number of polymerization-active H atoms per
molecule) of 1 to 8, preferably of 2 to 6 and particularly
preferably of 2 to 4. The H-functional starter compounds are used
either individually or as a mixture of at least two H-functional
starter compounds.
[0043] Preferred H-functional starter compounds are alcohols having
a composition according to general formula (I),
HO--(CH.sub.2).sub.x--OH
wherein x is from 1 to 20, preferably an even number from 2 to 20.
Examples of alcohols according to formula (I) are ethylene glycol,
1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and
1,12-dodecanediol. Further preferred H-functional starter compounds
are neopentyl glycol, trimethylolpropane, glycerol,
pentaerythritol, reaction products of the alcohols of formula (VII)
with .epsilon.-caprolactone, for example reaction products of
trimethylolpropane with .epsilon.-caprolactone, reaction products
of glycerol with .epsilon.-caprolactone and reaction products of
pentaerythritol with .epsilon.-caprolactone. Preferably employed
H-functional starter compounds further include water, diethylene
glycol, dipropylene glycol, castor oil, sorbitol and polyether
polyols constructed from repeating polyalkylene oxide units.
[0044] It is particularly preferable when the H-functional starter
compounds are one or more compounds selected from the group
consisting of ethylene glycol, propylene glycol, 1,3-propanediol,
1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,
2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol,
diethylene glycol, dipropylene glycol, glycerol,
trimethylolpropane, di- and trifunctional polyether polyols,
wherein the polyether polyol is constructed from a di- or
tri-H-functional starter compound and propylene oxide or a di- or
tri-H-functional starter compound, propylene oxide and ethylene
oxide. The polyether polyols preferably have an OH functionality of
2 to 4 and a molecular weight M.sub.n in the range from 62 to 8000
g/mol, preferably a molecular weight and more preferably of
.gtoreq.92 to .ltoreq.2000 g/mol.
[0045] A further embodiment of the invention may employ
polyacetals, preferably polymeric formaldehyde compounds, as
H-functional starter compounds for the process according to the
invention, oligomeric and polymeric forms of formaldehyde having at
least one terminal hydroxyl group for reaction with the compound
(A) being suitable in principle. According to the invention, the
term "terminal hydroxyl group" is to be understood as meaning in
particular a terminal hemiacetal functionality which is formed as a
structural feature by the polymerization of formaldehyde. For
example the starter compounds may be oligomers and polymers of
formaldehyde of general formula (I), wherein n is an integer
.gtoreq.2 and wherein polymeric formaldehyde typically has n>8
repeating units.
[0046] Polymeric formaldehyde starter compounds suitable for the
process of the invention generally have molar masses of 62 to 30
000 g/mol, preferably of 62 to 12 000 g/mol, particularly
preferably of 242 to 6000 g/mol and very particularly preferably of
242 to 3000 g/mol, and comprise from 2 to 1000, preferably from 2
to 400, particularly preferably from 8 to 200 and very particularly
preferably from 8 to 100 oxymethylene repeating units. The starter
compounds employed in the process according to the invention
typically have a functionality (F) of 1 to 3, but in certain cases
may also have higher functionality, i.e. have a functionality of
>3. It is preferable to employ in the process according to the
invention open-chain polymeric formaldehyde starter compounds
having terminal hydroxyl groups and having a functionality of 1 to
10, preferably of 1 to 5, particularly preferably of 2 to 3.
[0047] Employed with very particular preference in the process
according to the invention are linear polymeric formaldehyde
starter compounds having a functionality of 2 (e.g. GRANUFORM.RTM.
from Ineos). The functionality F corresponds to the number of OH
end groups per molecule.
[0048] Production of the polymeric formaldehyde starter compounds
used for the process according to the invention may be carried out
by known processes (cf., for example, M. Haubs et al., 2012,
Polyoxymethylenes, Ullmann's Encyclopedia of Industrial Chemistry;
G. Reus et al., 2012, Formaldehyde, ibid.). The formaldehyde
starter compounds may in principle also be employed in the process
according to the invention in the form of a copolymer, wherein
comonomers included in the polymer in addition to formaldehyde are,
for example, 1,4-dioxane or 1,3-dioxolane. Further suitable
formaldehyde copolymers for the process according to the invention
are copolymers of formaldehyde and of trioxane with cyclic and/or
linear formals, for example butanediol formal, or epoxides. It is
likewise conceivable for higher homologous aldehydes, for example
acetaldehyde, propionaldehyde, etc, to be incorporated into the
formaldehyde polymer as comonomers. It is likewise conceivable for
formaldehyde starter compounds according to the invention to in
turn be prepared from H-functional starter compounds; obtainable
here in particular through the use of polyfunctional starter
compounds are polymeric formaldehyde starter compounds having a
hydroxyl end group functionality F>2 (cf., for example, WO
1981001712 A1, Bull. Chem. Soc. J., 1994, 67, 2560-2566, U.S. Pat.
No. 3,436,375, JP 03263454, JP 2928823).
[0049] Also employable for the process according to the invention
are mixtures of different polymeric formaldehyde starter compounds
or mixtures with other H-functional starter compounds. Employable
as a suitable H-functional starter compound (starters) are
compounds having alkoxylation-active H atoms which have a molar
mass of 18 to 4500 g/mol, preferably of 62 to 2500 g/mol and
particularly preferably of 62 to 1000 g/mol. Alkoxylation-active
groups having active H atoms include, for example, --OH, --NH.sub.2
(primary amines), --NH-- (secondary amines), --SH, and --CO.sub.2H,
preference being given to --OH and --NH.sub.2, particular
preference being given to --OH. Employed as the H-functional
starter compound are for example one or more compounds selected
from the group consisting of mono- and polyvalent alcohols,
polyvalent amines, polyvalent thiols, amino alcohols, thio
alcohols, hydroxy esters, polyether polyols, polyester polyols,
polyester ether polyols, polyether carbonate polyols, polycarbonate
polyols, polycarbonates, polyethyleneimines, polyetheramines,
polytetrahydrofurans (e.g. PolyTHF.RTM. from BASF),
polytetrahydrofuran amines, polyether thiols, polyacrylate polyols,
castor oil, the mono- or diglyceride of ricinoleic acid,
monoglycerides of fatty acids, chemically modified mono-, di-
and/or triglycerides of fatty acids, and C1-C24 alkyl fatty acid
esters containing an average of at least 2 OH groups per
molecule.
[0050] As is well known, polymerization of formaldehyde already
proceeds due to the presence of small traces of water. In aqueous
solution a mixture of oligomers and polymers of different chain
lengths which are in equilibrium with molecular formaldehyde and
formaldehyde hydrate is thus formed according to the concentration
and the temperature of the solution. So-called paraformaldehyde
here precipitates out of the solution as a white, poorly soluble
solid and is generally a mixture of linear formaldehyde polymers
where n=8 to 100 oxymethylene repeating units.
[0051] One advantage of the process according to the invention is
in particular that polymeric formaldehyde/so-called
paraformaldehyde, which is an inexpensive and commercially
available product and moreover has a low carbon footprint, may be
used directly as a starter compound without any need for additional
preparatory steps here. An advantageous embodiment of the invention
thus employs paraformaldehyde as the starter compound. In
particular the molecular weight and the end group functionality of
the polymeric formaldehyde starter compound make it possible to
introduce polyoxymethylene blocks of defined molar weight and
functionality into the product.
[0052] The length of the polyoxymethylene block may here
advantageously be controlled in simple fashion in the process
according to the invention via the molecular weight of the employed
formaldehyde starter compound. Preferably employed here are linear
formaldehyde starter compounds of general formula (I), wherein n is
an integer.gtoreq.2, preferably where n=2 to 1000, particularly
preferably where n=2 to 400 and very particularly preferably where
n=8 to 100, having two terminal hydroxyl groups. Also employable as
starter compounds are in particular mixtures of polymeric
formaldehyde compounds of formula (I) each having different values
of n. In an advantageous embodiment the employed mixtures of
polymeric formaldehyde starter compounds of formula (I) contain at
least 1% by weight, preferably at least 5% by weight and
particularly preferably at least 10% by weight of polymeric
formaldehyde compounds where n.gtoreq.20.
[0053] In one embodiment of the process according to the invention
the molar ratio of the compound (A) to the H-functional starter
compound (BH) in the resulting addition product is .gtoreq.1,
preferably 1 to 200, particularly preferably 1-150.
n-protic Bronsted Acid (C)
[0054] In the context of the present invention the term "organic,
n-protic Bronsted acid (C)" is to be understood as meaning an
organic, non-polymeric compound constructed from carbon, hydrogen
and oxygen and optionally a further heteroatom distinct from the
abovementioned atoms, preferably containing a further heteroatom.
In line with the customary definition in the art Bronsted acids are
to be understood as meaning substances which may transfer protons
to a second reaction partner, the so-called Bronsted base,
typically in an aqueous medium at 25.degree. C. In the process
according to the invention the maximum number of transferable
protons n is n.gtoreq.2, preferably n=2, 3 or 4, particularly
preferably n=2 or 3, very particularly preferably n=2, wherein n is
an element of the natural numbers. The calculated proton fraction
of the organic, n-protic Bronsted acid (C) corresponds to the
degree of protolysis D and in the process according to the
invention is 0<D<n. For diprotic acids where n=2 the degree
of protolysis D is preferably 0.2 to 1.9, particularly preferably
0.5 to 1.8 and very particularly preferably 0.8 to 1.8. For
triprotic acids where n=3 the degree of protolysis D is preferably
0.3 to 2.8, particularly preferably 0.7 to 2.5 and very
particularly preferably 1.1 to 2.1. For tetraprotic acids where n=4
the degree of protolysis D is preferably 0.4 to 3.7, particularly
preferably 0.8 to 3.5 and very particularly preferably 1.1 to
3.1.
[0055] In embodiment the invention relates to a process wherein the
compound (C) is a non-polymeric compound.
[0056] In embodiment the invention relates to a process, wherein
the organic, n-protic Bronsted acid (C) has a calculated molar mass
of .ltoreq.1200 g/mol, preferably of .ltoreq.1000 g/mol and
particularly preferably of .ltoreq.850 g/mol.
[0057] In embodiment the invention relates to a process, wherein
the organic, n-protic Bronsted acid (C) has a calculated molar mass
of .gtoreq.90 g/mol, preferably of .gtoreq.100 g/mol and
particularly preferably of .gtoreq.110 g/mol.
[0058] In embodiment the invention relates to a process, wherein
the organic, n-protic Bronsted acid (C) has a calculated molar mass
of .gtoreq.90 g/mol to .ltoreq.1200 g/mol, preferably of .gtoreq.90
g/mol to .ltoreq.1000 g/mol and particularly preferably of
.gtoreq.100 g/mol to .ltoreq.850 g/mol.
[0059] In one embodiment of the process according to the invention
the organic, n-protic Bronsted acid (C) is a sulfonic acid, wherein
in line with the customary definition in the art a sulfonic acid is
to be understood as meaning an organic sulfur compounds having the
general structure R--SO.sub.2--OH, wherein R is an organic radical.
Here R--SO.sub.2--OH or, for short, R--SO.sub.3H represents the
sulfonic acid and R--SO.sub.3.degree. represents the deprotonated
sulfonate group formed by proton donation to a second reaction
partner, the so-called Bronsted base. The organic radical R
corresponds to linear cyclic or linear branched alkylene group
having 1 to 22 carbon atoms optionally containing further
heteroatoms and/or aryl groups having 5 to 18 carbon atoms
optionally containing further heteroatoms.
[0060] In a preferred embodiment substituted or unsubstituted
aromatic non-polymeric polysulfonic acids having a maximum number
of transferable protons n of n=2, 3 oder 4 are employed. In a
particularly preferred embodiment substituted or unsubstituted
naphthalenepolysulfonic acids where n=2 or 3 and/or substituted or
unsubstituted benzenepolysulfonic acids where n=2 or 3 are
employed. It is very particularly preferable when
1,5-naphthalenedisulfonic acids, 2,6-naphthalenedisulfonic acids
and/or 1,3-benzenedisulfonic acids where n=2 are. For diprotic
sulfonic acids where n=2 the degree of protolysis D is preferably
0.2 to 1.9, particularly preferably 0.5 to 1.8 and very
particularly preferably 0.8 to 1.8. For triprotic sulfonic acids
where n=3 the degree of protolysis D is preferably 0.3 to 2.8,
particularly preferably 0.7 to 2.5 and very particularly preferably
1.1 to 2.1. For tetraprotic sulfonic acids where n=4 the degree of
protolysis D is preferably 0.4 to 3.7, particularly preferably 0.8
to 3.5 and very particularly preferably 1.1 to 3.1.
[0061] In embodiment the invention relates to a process, wherein
the sulfonic acid has a calculated molar mass of .gtoreq.160 g/mol
to .ltoreq.1200 g/mol, preferably of .gtoreq.200 g/mol to
.ltoreq.1000 g/mol and particularly preferably of .gtoreq.230 g/mol
to .ltoreq.850 g/mol.
[0062] In one embodiment of the process according to the invention
the organic, n-protic Bronsted acid (C) having the degree of
protolysis 0<D<n is obtained by acid-base reactions with
proton transfer by [0063] (.alpha.) addition of suitable amounts of
suitable Bronsted bases (E) to the organic, n-protic Bronsted acids
or [0064] (.beta.) addition of suitable amounts of suitable
Bronsted acids (E'H) to the salts of the organic, n-protic Bronsted
acids.
Step .alpha.
[0065] In a preferred embodiment of step (.alpha.) the organic,
n-protic Bronsted acid (C) having the degree of protolysis
0<D<n is obtained by acid-base reactions with proton transfer
by addition of suitable amounts of a suitable Bronsted base (E) to
the completely or partially protonated organic, n-protic Bronsted
acid, wherein a suitable Bronsted base (E) has a greater base
strength K.sub.b(E) and thus a smaller pK.sub.b(E) than the
completely or partially protonated organic, n-protic Bronsted acid.
The suitable amount of the Bronsted base (E) is derived for example
from the desired degree of protolysis (D) of the organic, n-protic
Bronsted acid (C) and/or the base strength K.sub.b(E) of the
employed Bronsted base (E).
[0066] Such an organic, n-protic Bronsted acid (C) having a degree
of protolysis (D) in the range 0<D<n is obtainable for
example by reaction of completely or partially protonated organic,
n-protic Bronsted acids, preferably completely protonated sulfonic
acids, by addition of Bronsted bases (E) having a pK.sub.b(E) of
.ltoreq.10, preferably having a pK.sub.b(E) of .ltoreq.8 and very
particularly preferably having a pK.sub.b(E) of .ltoreq.5. It is
particularly preferable when disulfonic acids are reacted with
metal orthovanadates, metal tungstates, metal
hydrogentriphosphates, metal hydrogenphospates, metal sulfites,
metal trithiocarbonates, metal carbonates, metal
hydrogencarbonates, alkali metal hydroxides, alkaline earth metal
hydroxides, titanium hydroxide, zinc hydroxide, aluminum hydroxide,
vanadium and vanadyl hydroxides, iron(II) and iron(III) hydroxides,
bismuth(III) hydroxide, gallium(III) hydroxide, copper(II)
hydroxide, manganese(II) hydroxide, silver hydroxide, ammonium
hydroxides, phosphonium hydroxides, sulfonium hydroxides,
sulfoxonium hydroxides, alkali metal alkoxides, alkaline earth
metal alkoxides, titanium alkoxides, zinc alkoxides, aluminum
alkoxide, ammonium alkoxides, phosphonium alkoxides,
sulfoniumalkoxides, sulfoxonium alkoxides, alkali metal
alkoxylates, alkaline earth metal alkoxylates, titanium
alkoxylates, zinc alkoxylates, aluminum alkoxylate, ammonium
alkoxylates, phosphonium alkoxylates, sulfonium alkoxylates,
sulfoxonium alkoxylates, metal benzoates, metal acetates, metal
phenyolates, hydrazine, methyl- and ethylhydrazine, metal azides,
hydroxylamine, ammonia, substituted aliphatic and cycloaliphatic
mono-/di-/triamines with primary, secondary or tertiary amine
functions, lithium diisopropylamide, lithium organyls, amidine
bases, amides, alkali metal hydrides, alkaline earth metal
hydrides, titanium hydrides, zinc hydrides, aluminum hydride,
ammonium hydrides, phosphonium hydrides, sulfoniumhydrides and/or
sulfoxonium hydrides as Bronsted bases (E) to afford the organic,
n-protic Bronsted acid (C) having a degree of protolysis (D) in the
range 0<D<n. It is very particularly preferable when
benzene-1,3-disulfonic acid, naphthalene-1,5-disulfonic acid and/or
naphthalene-2,6-disulfonic acid are reacted with lithium
hydroxides, sodium hydroxides, potassium hydroxides, rubidium
hydroxides, cesium hydroxides, magnesium hydroxides, calcium
hydroxides, strontium hydroxides, barium hydroxides, scandium
hydroxides, titanium hydroxides, zinc hydroxides, aluminum
hydroxides, aliphatic primary ammonium hydroxides, aliphatic
secondary ammonium hydroxides, aliphatic tertiary ammonium
hydroxides, aliphatic quaternary ammonium hydroxides, phosphonium
hydroxides, aliphatic primary ammonium alkoxides, aliphatic
secondary ammonium alkoxides, aliphatic tertiary ammonium
alkoxides, aliphatic quaternary ammonium alkoxides, phosphonium
alkoxides, butylithium, potassium tert-butoxide,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo(4.3.0)non-5-ene (DBN) and/or primary, secondary
and tertiary aliphatic and cycloaliphatic mono- and diamines,
preferably with sodium hydroxide, potassium hydroxide, lithium
hydroxide, magnesium hydroxide, calcium hydroxide, aliphatic
quaternary ammonium alkoxides, phosphonium alkoxides, ammonia,
triethylamine, trimethylamine, diethylamine, propylamine,
methylamine, dimethylamine, ethylamine, ethylenediamine,
1,3-diaminopropanes, putrescine, 1,5-diaminopentane,
hexamethylenediamine, 1,2-diaminopropanes, diaminocyclohexane,
n-propylamine, di-n-propylamine, tri-n-propylamin, isopropylamine,
diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine,
diisobutylamine, 2-aminobutane, 2-ethylhexylamine,
di-2-ethylhexylamine, cyclohexylamine, dicyclohexylamine,
dimethylaminopropylamine, triethylenediamine,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), particularly preferably
with sodium hydroxide, potassium hydroxide, lithium hydroxide,
magnesium hydroxide, tetra(n-butyl)ammonium methoxide,
tetra(n-butyl)ammonium ethoxide and/or tetra(n-butyl)ammonium
isopropoxide, as Bronsted bases (E) to afford the organic, n-protic
Bronsted acid (C) having a degree of protolysis (D) in the range
0<D<n.
[0067] The acid-base reactions due to the addition of the Bronsted
base (E) to the completely or partially protonated organic,
n-protic Bronsted acid result not only in the formation of the
organic, n-protic Bronsted acid (C) where 0<D<n but also in
the formation of the corresponding Bronsted acid (EH) by proton
acceptance, wherein the corresponding Bronsted acids (EH) formed
are preferably alcohols or water and very preferably water,
methanol, isopropanol or ethanol.
[0068] In a particularly preferred embodiment of (.alpha.) the
formation of the organic, n-protic Bronsted acid (C) in step
(.alpha.) is or is not followed by a separation of the
corresponding Bronsted acid (EH) which is formed from the Bronsted
base (E) by proton acceptance. It is preferable when the
corresponding Bronsted acid (EH) is separated by distillation.
Step .beta.
[0069] In a preferred embodiment of step (.beta.) the organic,
n-protic Bronsted acid (C) having the degree of protolysis
0<D<n is obtained by acid-base reactions with proton transfer
by a suitable Bronsted acid (E'H) to the salts of the partially or
completely deprotonated organic, n-protic Bronsted acid, wherein a
suitable Bronsted acid (E'H) has a greater acid strength
K.sub.a(E'H) and thus a smaller pK.sub.a(E'H) than the completely
or partially deprotonated organic, n-protic Bronsted acid. The
suitable amount of the Bronsted acid (E'H) is derived for example
from the desired degree of protolysis (D) of the organic, n-protic
Bronsted acid (C) and/or the acid strength K.sub.a(E'H) of the
employed Bronsted acid (E'H).
[0070] For example such an organic, n-protic Bronsted acid (C)
having a degree of protolysis (D) in the range 0<D<n may be
obtained by reaction of a completely or partially deprotonated
metal salt of an organic, n-protic Bronsted acid, preferably a
metal salt of a sulfonic acid, by addition of strong Bronsted acid
(E'H) having a pK.sub.a(E'H) of .ltoreq.1. It is particularly
preferable when dialkali metal salts and/or diammonium salts of a
disulfonic acid are reacted with strong organic and/or inorganic
Bronsted acids (E'H) having a pK.sub.a(E'H) of .ltoreq.1 to afford
the organic, n-protic Bronsted acid (C) having a degree of
protolysis (D) in the range 0<D<n. It is very particularly
preferable when the disodium and/or the dipotassium salts of
benzene-1,3-disulfonic acid, naphthalene-1,5-disulfonic acid and/or
naphthalene-2,6-disulfic acid are reacted with aliphatic and
aromatic fluorinated sulfonic acids, trifluoromethanesulfonic acid,
perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic
acid, fluorosulfonic acid, bis(trifluoromethane)sulfonimide,
hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid,
sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic
acid, paratoluenesulfonic acid, aromatic sulfonic acids, aliphatic
sulfonic acids, preferably with trifluoromethanesulfonic acid,
perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic
acid, fluorosulfonic acid, bis(trifluoromethane)sulfonimide,
hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid,
sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic
acid, paratoluenesulfonic acid, methanesulfonic acid,
paratoluenesulfonic acid and particularly preferably with
trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid,
hydrobromic acid, hydroiodic acid,
bis(trifluoromethane)sulfonimide, pentacyanocyclopentadiene,
sulfuric acid, nitric acid, trifluoroacetic acid, to afford the
organic, n-protic Bronsted acid (C) having a degree of protolysis
(D) in the range 0<D<n.
[0071] The acid-base reactions due to the addition of the Bronsted
acid (E'H) to the completely or partially deprotonated organic,
n-protic Bronsted acid result not only in the formation of the
organic, n-protic Bronsted acid (C) where 0<D<n but also in
the formation of the corresponding Bronsted base (E') by proton
donation, wherein the corresponding Bronsted acids (EH) formed are
preferably metal salts, phosphonium salts or ammonium salts and
particularly preferably alkali metal salts or ammonium salts and
very preferably sodium hydrogensulfate, potassium hydrogensulfate,
lithium hydrogensulfate, sodium triflate, potassium triflate,
lithium triflate and/or ammonium triflate.
[0072] In a particularly preferred embodiment the formation of the
organic, n-protic Bronsted acid (C) in step (.beta.) is or is not
followed by a separation of the corresponding Bronsted base (E')
which is formed from the Bronsted base (E') by proton donation. It
is preferable when the corresponding Bronsted acid (E') is not
separated.
[0073] In a further embodiment of the process the organic, n-protic
Bronsted acid (C) is employed in an amount of 0.0001 mol % to 10
mol % based on the amount of substance of the compound (BH).
[0074] In a further embodiment of the process according to the
invention the addition of the compound (A) onto the H-functional
starter compound (BH) in the presence of the organic, n-protic
Bronsted acid (C) is performed under the mildest possible reaction
temperatures of 20.degree. C. to 180.degree. C. in order to reduce
for example decomposition reactions or undesired side reactions of
chemically/thermally labile H-functional starter compounds (BH)
such as for example polycarbonate polyols or polyacetal compounds.
The reaction of the compound (BH) with (A) in the presence of the
organic, n-protic Bronsted acid (C) may be carried out under
isothermal or adiabatic conditions optionally with a defined
temperature profile.
[0075] In a further embodiment of the process according to the
invention the addition of the compound (A) onto the H-functional
starter compound (BH) in the presence of the organic, n-protic
Bronsted acid (C) is performed in reaction times of up to 24 h,
preferably up to 20 h, particularly preferably up to 12 h.
[0076] In a further embodiment the process may be performed in a
batch mode, semi-batch mode or continuous mode.
[0077] In a further embodiment of the process according to the
invention the addition of the compound (A) onto the H-functional
starter compound (BH) in the presence of the organic, n-protic
Bronsted acid (C) is performed solventlessly or in a solvent.
Preferred solvents are polar or nonpolar aprotic solvents.
Particular preference is given to solvents selected from the group
consisting of cyclic propylene carbonate, ethyl acetate, iso-propyl
acetate, n-butyl acetate, tetrahydrofuran, 1,3-dioxolane,
1,3,5-trioxepane, 1,4-dioxane, dimethyldioxane, methyl phenyl ether
and toluene.
[0078] In a further embodiment of the process according to the
invention the organic, n-protic Bronsted acid (C) may also be
produced directly in the presence of the starter (BH) in the
presence or absence of a further solvent. Preferably employed here
are chlorinated solvents and particularly preferably
dichloromethane and/or chloroform.
[0079] In embodiment the invention relates to an n-protic Bronsted
acid (C), wherein the n-protic Bronsted acid (C) has a calculated
molar mass of .gtoreq.90 g/mol to .ltoreq.1200 g/mol, preferably of
.gtoreq.100 g/mol to .ltoreq.1000 g/mol and particularly preferably
of .gtoreq.110 g/mol to .ltoreq.850 g/mol.
[0080] The invention also provides a ring-opening product,
preferably of a polyvalent alcohol, polyvalent amine, polyvalent
thiol, amino alcohol, thioalcohol, hydroxyester, polyether polyol,
polyester polyol, polyester ether polyol, polyether carbonate
polyol, polycarbonate polyol, polycarbonate, polymeric formaldehyde
compound, polyamide, obtainable by a process as described in the
preceding pages.
[0081] A further aspect of the invention is a polyurethane polymer
obtainable by reaction comprising the ring-opening product
according to the invention, preferably a polyvalent alcohol,
polyvalent amine, polyvalent thiol, amino alcohol, thioalcohol,
hydroxyester, polyether polyol, polyester polyol, polyester ether
polyol, polyether carbonate polyol, polycarbonate polyol,
polycarbonate, polymeric formaldehyde compound, polyamide, with an
isocyanate component comprising a polyisocyanate.
[0082] The isocyanate may be an aliphatic or aromatic di- or
polyisocyanate. Examples include 1,4-butylene diisocyanate,
1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate (HDI) and
dimers, trimers, pentamers, heptamers or nonamers or mixtures
thereof, isophorone diisocyanate (IPDI), 2,2,4- and/or
2,4,4-trimethylhexamethylene diisocyanate, the isomeric
bis(4,4'-isocyanatocyclohexyl)methanes or mixtures thereof with any
desired isomer content, 1,4-cyclohexylene diisocyanate,
1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate
(TDI), 1,5-naphthylene diisocyanate, 2,2'- and/or 2,4'- and/or
4,4'-diphenylmethane diisocyanate (MDI) and/or higher homologs
(polymeric MDI), 1,3- and/or 1,4-bis(2-isocyanatoprop-2-yl)benzene
(TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), and also alkyl
2,6-diisocyanatohexanoates (lysine diisocyanates) having C1 to
C6-alkyl groups. Preference is given here to an isocyanate from the
diphenylmethane diisocyanate series.
[0083] In addition to the abovementioned polyisocyanates, it is
also possible to use proportions of modified diisocyanates of
uretdione, isocyanurate, urethane, carbodiimide, uretonimine,
allophanate, biuret, amide, iminooxadiazinedione and/or
oxadiazinetrione structure and also unmodified polyisocyanate
having more than 2 NCO groups per molecule, for example
4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate)
or triphenylmethane 4,4',4''-triisocyanate.
[0084] It is possible for the isocyanate to be a prepolymer
obtainable by reaction of an isocyanate having an NCO functionality
of .gtoreq.2 and ring-opening products, preferably of a polyvalent
alcohol, polyvalent amine, polyvalent thiol, amino alcohol,
thioalcohol, hydroxyester, polyether polyol, polyester polyol,
polyester ether polyol, polyether carbonate polyol, polycarbonate
polyol, polycarbonate, polymeric formaldehyde compound, polyamide,
and having a molecular weight of .gtoreq.62 g/mol to .ltoreq.8000
g/mol and OH functionalities of .gtoreq.1.5 to .ltoreq.6.
[0085] The invention further provides an n-protic Bronsted acid (C)
having a degree of protolysis D 0<D<n, wherein n is the
maximum number of transferable protons where n=2, 3 or 4 and D is
the calculated proton fraction of the organic, n-protic Bronsted
acid (C),
characterized in that acids where n=2 is 0.2 to 1.9, for triprotic
acid where n=3 is 0.3 to 2.8, for tetraprotic acids where n=4 is
0.4 to 3.7, wherein the organic, n-protic Bronsted acid (C) having
the degree of protolysis 0<D<n is obtained by acid-base
reactions with proton transfer by [0086] (.alpha.) addition of
suitable amounts of at least one suitable Bronsted base (E) to the
at least one organic, n-protic Bronsted acid, wherein the Bronsted
base (E) contains at least one cation (F) selected from the group
consisting of alkali metal-containing, alkaline earth
metal-containing, metalloid-containing, transition
metal-containing, lanthanoid metal-containing, aliphatic
ammonium-containing and phosphonium-containing and
sulfonium-containing cations or [0087] (.beta.) addition of
suitable amounts of at least one suitable Bronsted acid (E'H) to
the salt of the at least one organic, n-protic Bronsted acid,
wherein the salts of the organic, n-protic Bronsted acid contain at
least one cation (F') selected from the group consisting of alkali
metal-containing, alkaline earth metal-containing,
metalloid-containing, transition metal-containing, lanthanoid
metal-containing, aliphatic ammonium-containing and
phosphonium-containing and sulfonium-containing cations.
[0088] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the cation (F) is selected from the
group consisting of lithium cation, sodium cation, potassium
cation, rubidium cation, cesium cation, magnesium cation, calcium
cation, strontium cation, barium cation, scandium cation, titanium
cation, zinc cation, aluminum cation, aliphatic primary ammonium
ions, aliphatic secondary ammonium ions, aliphatic tertiary
ammonium ions, aliphatic quaternary ammonium ions, phosphonium
ions, sulfonium ions and sulfoxonium ions, preferably from lithium
cation, sodium cation, potassium cation, magnesium cation, calcium
cation, quaternary ammonium ions and triphenylphosphonium ions and
particularly preferably from sodium cation, potassium cation,
magnesium cation and n-butylammonium ion.
[0089] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the cation (F') is selected from the
group consisting of lithium cation, sodium cation, potassium
cation, rubidium cation, cesium cation, magnesium cation, calcium
cation, strontium cation, barium cation, scandium cation, titanium
cation, zinc cation, aluminum cation, aliphatic primary ammonium
ions, aliphatic secondary ammonium ions, aliphatic tertiary
ammonium ions, aliphatic quaternary ammonium ions, phosphonium
ions, sulfonium ions and sulfoxonium ions, preferably from lithium
cation, sodium cation, potassium cation, magnesium cation, calcium
cation, quaternary ammonium ions and triphenylphosphonium ions and
particularly preferably from sodium cation, potassium cation,
magnesium cation and n-butylammonium ion.
[0090] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the at least one Bronsted base (E) is
selected from the group consisting of lithium hydroxide, sodium
hydroxide, potassium hydroxide, rubidium hydroxide, cesium
hydroxide, magnesium hydroxide, calcium hydroxide, strontium
hydroxide, barium hydroxide, scandium hydroxide, titanium
hydroxide, zinc hydroxide, aluminum hydroxide, aliphatic primary
ammonium hydroxides, aliphatic secondary ammonium hydroxides,
aliphatic tertiary ammonium hydroxides, aliphatic quaternary
ammonium hydroxides, phosphonium hydroxides, aliphatic primary
ammonium alkoxides, aliphatic secondary ammonium alkoxides,
aliphatic tertiary ammonium alkoxides, aliphatic quaternary
ammonium alkoxides, phosphonium alkoxides, butylithium, potassium
tert-butoxide, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), primary aliphatic amines,
secondary aliphatic amines, tertiary aliphatic amines, primary
cycloaliphatic amines, secondary cycloaliphatic amines, tertiary
cycloaliphatic amines and phosphonium alkoxides, preferably from
sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium
hydroxide, calcium hydroxide, aliphatic quaternary ammonium
alkoxides, phosphonium alkoxides, ammonia, triethylamine,
trimethylamine, diethylamine, propylamine, methylamine,
dimethylamine, ethylamine, ethylenediamine, 1,3-diaminopropanes,
putrescine, 1,5-diaminopentane, hexamethylenediamine,
1,2-diaminopropanes, diaminocyclohexane, n-propylamine,
di-n-propylamine, tri-n-propylamine, isopropylamine,
diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine,
diisobutylamine, 2-aminobutane, 2-ethylhexylamine,
di-2-ethylhexylamine, cyclohexylamine, dicyclohexylamine,
dimethylaminopropylamine, triethylenediamine,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), particularly preferably
from sodium hydroxide, potassium hydroxide, lithium hydroxide,
magnesium hydroxide, tetra(n-butyl)ammonium methoxide,
tetra(n-butyl)ammonium ethoxide and tetra(n-butyl)ammonium
isopropoxide.
[0091] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the at least one Bronsted acid (E'H) is
selected from the group consisting of aliphatic fluorinated
sulfonic acids, aromatic fluorinated sulfonic acids,
trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid,
hydrobromic acid, hydroiodic acid, fluorosulfonic acid,
bis(trifluoromethane)sulfonimide, hexafluorantimonic acid,
pentacyanocyclopentadiene, picric acid, sulfuric acid, nitric acid,
trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic
acid, aromatic sulfonic acids and aliphatic sulfonic acids,
preferably from trifluoromethanesulfonic acid, perchloric acid,
hydrochloric acid, hydrobromic acid, hydroiodic acid,
fluorosulfonic acid, bis(trifluoromethane)sulfonimide,
hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid,
sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic
acid, paratoluenesulfonic acid, methanesulfonic acid and
paratoluenesulfonic acid, particularly preferably from
trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid,
hydrobromic acid, hydroiodic acid,
bis(trifluoromethane)sulfonimide, pentacyanocyclopentadiene,
sulfuric acid, nitric acid and trifluoroacetic acid.
[0092] In one embodiment of the n-protic Bronsted acid (C)
according to the invention a diprotic acid where n=2 having a
degree of protolysis D of 0.8 to 1.8, preferably 1.1 to 1.7, is
used.
[0093] In one embodiment the n-protic Bronsted acid (C) is at least
one sulfonic acid.
[0094] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the sulfonic acid is selected from the
group consisting of at least one substituted or unsubstituted
naphthalenepolysulfonic acid where n=2 or 3 and/or at least one
substituted or unsubstituted benzenepolysulfonic acid where n=2 or
3.
[0095] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the degree of protolysis D of the
sulfonic acid for diprotic acids where n=2 is 0.8 to 1.8 and for
triprotic acids where n=3 is 1.1 to 2.1.
[0096] In one embodiment of the n-protic Bronsted acid (C)
according to the invention the sulfonic acid is selected from the
group consisting of 1,5-naphthalenedisulfonic acid,
2,6-naphthalenedisulfonic acid and 1,3-benzenedisulfonic acid,
preferably 1,5-naphthalenedisulfonic acid,
2,6-naphthalenedisulfonic acid and very particularly preferably
2,6-naphthalenedisulfonic acid, wherein in a preferred embodiment
the degree of protolysis D is 0.8 to 1.8, preferably 1.1 to
1.7.
[0097] In a further embodiment the n-protic Bronsted acid (C) is
used as a catalyst, additive, for example as a foaming
agent/stabilizer or starter, preferably as a catalyst.
[0098] In a first embodiment the invention relates to a process for
addition of a compound (A) onto an H-functional starter compound
(BH) in the presence of a catalyst, wherein the at least one
compound (A) is selected from at least one group consisting of
alkylene oxide (A-1), lactone (A-2), lactide (A-3), cyclic acetal
(A-4), lactam (A-5), cyclic anhydrides (A-6) and oxygen-containing
heterocyclic compound (A-7) distinct from (A-1), (A-2), (A-3),
(A-4) and (A-6), wherein the catalyst comprises an organic,
n-protic Bronsted acid (C), wherein n.gtoreq.2 and is an element of
the natural numbers and the degree of protolysis D is 0<D<n
where n is the maximum number of transferable protons and D is the
calculated proton fraction of the organic, n-protic Bronsted acid
(C).
[0099] In a second embodiment the invention relates to a process
according to the first embodiment, wherein the compound (A) is
selected from at least one group consisting of alkylene oxide
(A-1), lactone (A-2), cyclic acetal (A-4) and cyclic anhydride
(A-6).
[0100] In a third embodiment, the invention relates to a process
according to the first or second embodiment, wherein the organic,
n-protic Bronsted acid (C) is a sulfonic acid.
[0101] In a fourth embodiment the invention relates to a process
according to any of the first to third embodiments, wherein the
maximum number of transferable protons n is n=2, 3 or 4.
[0102] In a fifth embodiment the invention relates to a process
according to the fourth embodiment, wherein the degree of
protolysis D for diprotic acids where n=2 is 0.2 to 1.9, for
triprotic acids where n=3 is 0.3 to 2.8 and for tetraprotic acids
where n=4 is 0.4 to 3.7.
[0103] In a sixth embodiment the invention relates to a process
according to any of the first to fifth embodiments, wherein the
organic, n-protic Bronsted acid (C) having the degree of protolysis
0<D<n is obtained by acid-base reactions with proton transfer
by [0104] (.alpha.) addition of suitable amounts of suitable
Bronsted bases (E) to the organic, n-protic Bronsted acids or
addition of suitable amounts of suitable Bronsted acids (E'H) to
the salts of the organic, n-protic Bronsted acids.
[0105] In a seventh embodiment the invention relates to a process
according to the sixth embodiment, wherein the organic, n-protic
Bronsted acid (C) having the degree of protolysis 0<D<n is
obtained by acid-base reactions with proton transfer in step [0106]
(.alpha.) by addition of Bronsted bases (E) having a pK.sub.b(E) of
.ltoreq.10, preferably having a pK.sub.b(E) of .ltoreq.8 and very
particularly preferably having a pK.sub.b(E) of .ltoreq.5 to the
completely protonated sulfonic acids or by addition of strong
Bronsted acids (E'H) having a pK.sub.a(E'H) of .ltoreq.1 to the
metal salt of a sulfonic acid.
[0107] In an eighth embodiment the invention relates to a process
according to any of the first to seventh embodiments, wherein the
at least one compound (A) is selected from the group consisting of
ethylene oxide, propylene oxide, styrene oxide, allyl glycidyl
ether, .epsilon.-caprolactone, propiolactone, .beta.-butyrolactone,
.gamma.-butyrolactone, .epsilon.-caprolactam, 1,3-dioxolane,
1,4-dioxane, tetrahydrofuran and 1,3,5-trioxane.
[0108] In a ninth embodiment the invention relates to a process
according to any of the first to eighth embodiments, wherein the
compound (BH) is selected from one or more compounds selected from
the group consisting of mono- or polyvalent alcohols, polyvalent
amines, polyvalent thiols, amino alcohols, thio alcohols, hydroxy
esters, polyether polyols, polyester polyols, polyester ether
polyols, polyether carbonate polyols, polycarbonate polyols,
polycarbonates, polyacetals, polymeric formaldehyde compounds,
polyethyleneimines, polyetheramines, polytetrahydrofurans,
polytetrahydrofuranamines, polyether thiols, polyacrylate polyols,
castor oil, the mono- or diglyceride of ricinoleic acid,
monoglycerides of fatty acids, chemically modified mono-, di-
and/or triglycerides of fatty acids and C1-C24 alkyl fatty acid
esters containing on average at least 2 OH groups per molecule.
[0109] In a tenth embodiment the invention relates to an n-protic
Bronsted acid (C) having a degree of protolysis D 0<D<n,
wherein n is the maximum number of transferable protons where n=2,
3 or 4 and D is the calculated proton fraction of the organic,
n-protic Bronsted acid (C), wherein the degree of protolysis D for
diprotic acids where n=2 is 0.2 to 1.9, for triprotic acids where
n=3 is 0.3 to 2.8 and for tetraprotic acids where n=4 is 0.4 to
3.7, wherein the organic, n-protic Bronsted acid (C) having the
degree of protolysis D 0<D<n is obtained by acid-base
reactions with proton transfer by [0110] (.alpha.) addition of
suitable amounts of at least one suitable Bronsted base (E) to the
at least one organic, n-protic Bronsted acid, wherein the Bronsted
base (E) contains at least one cation (F) selected from the group
consisting of alkali metal-containing, alkaline earth
metal-containing, metalloid-containing, transition
metal-containing, lanthanoid metal-containing, aliphatic
ammonium-containing and phosphonium-containing and
sulfonium-containing cations. or [0111] (.beta.) addition of
suitable amounts of at least one suitable Bronsted acid (E'H) to
the salt of the at least one organic n-protic Bronsted acid,
wherein the salts of the organic n-protic Bronsted acid contains at
least one cation (F') selected from the group consisting of alkali
metal-containing, alkaline earth metal-containing,
metalloid-containing, transition metal-containing, lanthanoid
metal-containing, aliphatic ammonium-containing and
phosphonium-containing and sulfonium-containing cations (b)
addition of suitable amounts of at least one suitable Bronsted acid
(E'H) to the salt of the at least one organic n-protic Bronsted
acid, wherein the salts of the organic n-protic Bronsted acid
contains at least one cation (F') selected from the group
consisting of alkali metal-containing, alkaline earth
metal-containing, metalloid-containing, transition
metal-containing, lanthanoid metal-containing, aliphatic
ammonium-containing and phosphonium-containing and
sulfonium-containing cations.
[0112] In an eleventh embodiment the invention relates to an
n-protic Bronsted acid (C) according to the tenth embodiment,
wherein the cation (F) is selected from the group consisting of
lithium cation, sodium cation, potassium cation, rubidium cation,
cesium cation, magnesium cation, calcium cation, strontium cation,
barium cation, scandium cation, titanium cation, zinc cation,
aluminum cation, aliphatic primary ammonium ions, aliphatic
secondary ammonium ions, aliphatic tertiary ammonium ions,
aliphatic quaternary ammonium ions, phosphonium ions, sulfonium
ions and sulfoxonium ions, preferably from lithium cation, sodium
cation, potassium cation, magnesium cation, calcium cation,
quaternary ammonium ions and triphenylphosphonium ions and
particularly preferably from sodium cation, potassium cation,
magnesium cation and n-butylammonium ion.
[0113] In a twelfth embodiment the invention relates to an n-protic
Bronsted acid (C) according to either of the tenth and eleventh
embodiments, wherein the cation (F') is selected from the group
consisting of lithium cation, sodium cation, potassium cation,
rubidium cation, cesium cation, magnesium cation, calcium cation,
strontium cation, barium cation, scandium cation, titanium cation,
zinc cation, aluminum cation, aliphatic primary ammonium ions,
aliphatic secondary ammonium ions, aliphatic tertiary ammonium
ions, aliphatic quaternary ammonium ions, phosphonium ions,
sulfonium ions and sulfoxonium ions, preferably from lithium
cation, sodium cation, potassium cation, magnesium cation, calcium
cation, quaternary ammonium ions and triphenylphosphonium ions and
particularly preferably from sodium cation, potassium cation,
magnesium cation and n-butylammonium ion.
[0114] In a thirteenth embodiment the invention relates to an
n-protic Bronsted acid (C) according to any of the tenth to twelfth
embodiments, wherein the at least one Bronsted base (E) is selected
from the group consisting of lithium hydroxide, sodium hydroxide,
potassium hydroxide, rubidium hydroxide, cesium hydroxide,
magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium
hydroxide, scandium hydroxide, titanium hydroxide, zinc hydroxide,
aluminum hydroxide, aliphatic primary ammonium hydroxides,
aliphatic secondary ammonium hydroxides, aliphatic tertiary
ammonium hydroxides, aliphatic quaternary ammonium hydroxides,
phosphonium hydroxides, aliphatic primary ammonium alkoxides,
aliphatic secondary ammonium alkoxides, aliphatic tertiary ammonium
alkoxides, aliphatic quaternary ammonium alkoxides, phosphonium
alkoxides, butylithium, potassium tert-butoxide,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), primary aliphatic amines,
secondary aliphatic amines, tertiary aliphatic amines, primary
cycloaliphatic amines, secondary cycloaliphatic amines, tertiary
cycloaliphatic amines and phosphonium alkoxides, preferably from
sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium
hydroxide, calcium hydroxide, aliphatic quaternary ammonium
alkoxides, phosphonium alkoxides, ammonia, triethylamine,
trimethylamine, diethylamine, propylamine, methylamine,
dimethylamine, ethylamine, ethylenediamine, 1,3-diaminopropanes,
putrescine, 1,5-diaminopentane, hexamethylenediamine,
1,2-diaminopropanes, diaminocyclohexane, n-propylamine,
di-n-propylamine, tri-n-propylamin, isopropylamine,
diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine,
diisobutylamine, 2-aminobutane, 2-ethylhexylamine,
di-2-ethylhexylamine, cyclohexylamine, dicyclohexylamine,
dimethylaminopropylamine, triethylenediamine,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and
1,5-diazabicyclo(4.3.0)non-5-ene (DBN), particularly preferably
from sodium hydroxide, potassium hydroxide, lithium hydroxide,
magnesium hydroxide, tetra(n-butyl)ammonium methoxide,
tetra(n-butyl)ammonium ethoxide and tetra(n-butyl)ammonium
isopropoxide.
[0115] In a fourteenth embodiment the invention relates to an
n-protic Bronsted acid (C) according to any of the tenth to twelfth
embodiments, wherein the at least one Bronsted acid (E'H) is
selected from the group consisting of aliphatic fluorinated
sulfonic acids, aromatic fluorinated sulfonic acids,
trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid,
hydrobromic acid, hydroiodic acid, fluorosulfonic acid,
bis(trifluoromethane)sulfonimide, hexafluorantimonic acid,
pentacyanocyclopentadiene, picric acid, sulfuric acid, nitric acid,
trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic
acid, aromatic sulfonic acids and aliphatic sulfonic acids,
preferably from trifluoromethanesulfonic acid, perchloric acid,
hydrochloric acid, hydrobromic acid, hydroiodic acid,
fluorosulfonic acid, bis(trifluoromethane)sulfonimide,
hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid,
sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic
acid, paratoluenesulfonic acid, methanesulfonic acid and
paratoluenesulfonic acid, particularly preferably from
trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid,
hydrobromic acid, hydroiodic acid,
bis(trifluoromethane)sulfonimide, pentacyanocyclopentadiene,
sulfuric acid, nitric acid and trifluoroacetic acid.
[0116] In a fifteenth embodiment the invention relates to an
n-protic Bronsted acid (C) according to any of the tenth to
fourteenth embodiments, wherein diprotic acids where n=2 having a
degree of protolysis D of 0.8 to 1.8, preferably 1.1 to 1.7, are
used.
[0117] In a sixteenth embodiment the invention relates to an
n-protic Bronsted acid (C) according to any of the tenth to
fifteenth embodiments, wherein the n-protic Bronsted acid (C) is at
least one sulfonic acid.
[0118] In a seventeenth embodiment the invention relates to a
sulfonic acid according to any of the tenth to sixteenth
embodiments, wherein the sulfonic acid is selected from the group
consisting of at least one substituted or unsubstituted
naphthalenepolysulfonic acid where n=2 or 3 and/or at least one
substituted or unsubstituted benzenepolysulfonic acid where n=2 or
3.
[0119] In an eighteenth embodiment the invention relates to a
sulfonic acid according to any of the tenth to seventeenth
embodiments, wherein the degree of protolysis D for diprotic acids
where n=2 is 0.8 to 1.8 and for triprotic acids where n=3 is 1.1 to
2.1.
[0120] In a nineteenth embodiment the invention relates to a
sulfonic acid according to any of the tenth to eighteenth
embodiments, wherein the at least one sulfonic acid is selected
from the group consisting of 1,5-naphthalenedisulfonic acid,
2,6-naphthalenedisulfonic acid and 1,3-benzenedisulfonic acid,
preferably 1,5-naphthalenedisulfonic acid,
2,6-naphthalenedisulfonic acid and very particularly preferably
2,6-naphthalenedisulfonic acid.
[0121] In a twentieth embodiment the invention relates to a
sulfonic acid according to the nineteenth embodiment, wherein the
degree of protolysis D is 0.8 to 1.8, preferably 1.1 to 1.7.
[0122] In a twenty-first embodiment the invention relates to the
use of the n-protic Bronsted acid (C) according to any of the tenth
to twentieth embodiments as catalyst.
[0123] In a twenty-second embodiment the invention relates to a
process according to any of the first to ninth embodiments, wherein
the compound (BH) is selected from the group consisting of
polyether carbonate polyols, polycarbonate polyols, polyether ester
carbonate polyols and polymeric formaldehyde compounds.
[0124] In a twenty-third embodiment the invention relates to a
process according to any of the first to ninth embodiments, wherein
the compound (C) is a non-polymeric compound.
[0125] In a twenty-fourth embodiment the invention relates to a
process according to any of the first to ninth, twenty-second and
twenty-third embodiments, wherein the organic, n-protic Bronsted
acid (C) has a calculated molar mass of .ltoreq.1200 g/mol,
preferably of .ltoreq.1000 g/mol and particularly preferably of
.ltoreq.850 g/mol.
[0126] In a twenty-fifth embodiment the invention relates to a
process according to any of the first to ninth, twenty-second to
twenty-fourth embodiments, wherein the organic, n-protic Bronsted
acid (C) has a calculated molar mass of .gtoreq.90 g/mol,
preferably of .gtoreq.100 g/mol and particularly preferably of
.gtoreq.110 g/mol.
[0127] In a twenty-sixth embodiment the invention relates to a
process according to any of the first to ninth, twenty-second to
twenty-fifth embodiments, wherein the organic, n-protic Bronsted
acid (C) has a calculated molar mass of .gtoreq.90 g/mol to
.ltoreq.1200 g/mol, preferably of .gtoreq.100 g/mol to .ltoreq.1000
g/mol and particularly preferably of .gtoreq.110 g/mol to
.ltoreq.850 g/mol.
[0128] In a twenty-seventh embodiment the invention relates to a
process according to any of the third to ninth embodiments, wherein
the sulfonic acid has a calculated molar mass of .gtoreq.160 g/mol
to <1200 g/mol, preferably of .gtoreq.200 g/mol to .ltoreq.1000
g/mol and particularly preferably of .gtoreq.230 g/mol to
.ltoreq.850 g/mol.
[0129] In a twenty-eighth embodiment the invention relates to an
n-protic Bronsted acid (C) according to any of the tenth to
twentieth embodiments, wherein the n-protic Bronsted acid (C) has a
calculated molar mass of .gtoreq.90 g/mol to .ltoreq.1200 g/mol,
preferably of .gtoreq.100 g/mol to .ltoreq.1000 g/mol and
particularly preferably of .gtoreq.110 g/mol to .ltoreq.850
g/mol.
[0130] In a twenty-ninth embodiment the invention relates to
ring-opening products obtainable by a process according to the
first to ninth, twenty-second to twenty-seventh embodiments.
[0131] In a thirtieth embodiment the invention relates to a
polyurethane polymer obtainable by reaction comprising an inventive
ring-opening product according to the twenty-ninth embodiment with
an isocyanate component comprising a polyisocyanate.
[0132] In a thirty-first embodiment the invention relates to a
sulfonic acid according to any of the sixteenth to twentieth
embodiments, wherein the sulfonic acid has a calculated molar mass
of .gtoreq.160 g/mol to .ltoreq.1200 g/mol, preferably of
.gtoreq.200 g/mol to .ltoreq.1000 g/mol and particularly preferably
of .gtoreq.230 g/mol to .ltoreq.850 g/mol.
EXAMPLES
[0133] The present invention is elucidated in detail by the figures
and examples which follow, but without being limited thereto.
Compounds (A)
[0134] Ethylene oxide (3.0, purity.gtoreq.99.9% by weight, Linde
AG) Propylene oxide (purity 99.9%, Chemogas GmbH) Styrene oxide
(purity 97%, Sigma-Aldrich Chemie GmbH) Allyl glycidyl ether
(purity 99%, Sigma-Aldrich Chemie GmbH) 1,3-Dioxolane (purity
99.8%, Sigma-Aldrich Chemie GmbH) .beta.-Butyrolactone (purity 98%,
Sigma-Aldrich Chemie GmbH) .epsilon.-Caprolactone (purity 97%,
Sigma-Aldrich Chemie GmbH) Maleic anhydride (purity 99%,
Sigma-Aldrich Chemie GmbH) Tetrahydrofuran (absolute, purity 99.9%,
Sigma-Aldrich Chemie GmbH)
Compounds (BH) Having at Least One Zerewitino-Active Hydrogen
Atom
PEG:
[0135] Polyethylene glycol having a molecular mass of 1000 g/mol
was obtained from Fluka. Before further use the commercially
available product was dried over phosphorus pentoxide in a
desiccator.
PET:
[0136] Polypropylene glycol (ARCOL.RTM. POLYOL 1004) having an
average molecular mass of 432 g/mol (hydroxyl number (OH number):
250-270 mg(KOH)/g) was obtained from Covestro AG. Before further
use the available product was dried under high vacuum.
PC: CONVERGE.RTM. Polyol 212-10, M=1000 g/mol:
[0137] Polycarbonate diol from Novomer Inc. CONVERGE.RTM. Polyol
212-10 obtainable by reaction of CO2 and propylene oxide having an
average molecular mass of 1000 g/mol, a CO2 fraction of about 40%
by weight, an OH number of 112 mg(KOH)/g. Analysis of the starting
material by proton resonance spectroscopy revealed a content of 3%
by weight of cyclic propylene carbonate (cPC).
pFA: Paraformaldehyde (M=450 g/mol)
[0138] Paraformaldehyde (trade name: Granuform 96) was obtained
from Ineos AG. The number-average molecular mass of the product is
specified as 450 g/mol.
Employed Catalysts/Starting Materials Thereof
[0139] 1,3-Benzenedisulfonic acid disodium salt: 1,3-Na2-BDS
(purity 94%, Sigma-Aldrich Chemie GmbH) 1,5-Naphthalenedisulfonic
acid disodium salt: 1,5-Na2-NDS (purity 95%, Sigma-Aldrich Chemie
GmbH) 2,6-Naphthalenedisulfonic acid disodium salt: 2,6-Na2-NDS
(purity 97%, Sigma-Aldrich Chemie GmbH) 1,5-Naphthalenedisulfonic
acid 1,5-NDS (purity 97%, Sigma-Aldrich Chemie GmbH) Sulfuric acid:
H.sub.2SO.sub.4 (purity 98%, Sigma-Aldrich Chemie GmbH)
Trifluoromethanesulfonic acid: CF.sub.3SO.sub.3H (purity 98%,
Sigma-Aldrich Chemie GmbH) Sodium triflate: NaOTf (purity 97%,
Sigma-Aldrich Chemie GmbH) Sodium hydrogensulfate: NaHSO.sub.4
(purity 90%, Sigma-Aldrich Chemie GmbH) Para-toluenesulfonic acid:
p-TSA (purity 98%, Sigma-Aldrich Chemie GmbH) Fumaric acid
C.sub.4H.sub.4O.sub.4: (purity 99%, Sigma-Aldrich Chemie GmbH)
Tetrabutylammonium methoxide solution: (n-Bu).sub.4N (OMe) (20%
methanol solution, Sigma-Aldrich Chemie GmbH)
1,8-Diazabicyclo[5.4.0]undec-7-ene: DBU (purity 98%, Sigma-Aldrich
Chemie GmbH) Perfluorosulfonic acid membrane: Nation.RTM. N117-type
in a thickness of 0.007 inch with equivalent amount of sulfonyl
groups of 0.91-1.11 mmol/g (manufacturer specifications for ion
exchange capacity IEC), Sigma-Aldrich Chemie GmbH
Description of the Methods:
[0140] Gel permeation chromatography (GPC): The measurements were
performed on an Agilent 1200 Series (G1310A Iso Pump, G1329A ALS,
G1316A TCC, G1362A RID, G1365D MWD), detection by RID; eluent:
tetrahydrofuran (GPC grade), flow rate 1.0 ml/min; column
combination: PSS SDV precolumn 8.times.50 mm (5 .mu.m), 2.times.PSS
SDV linear S 8.times.300 ml (5 .mu.m). Polystyrene of known molar
mass from "PSS Polymer Standards Service" were used for
calibration. The measurement recording and evaluation software used
was the "PSS WinGPC Unity" software package. The GPC chromatograms
were recorded in accordance with DIN 55672-1. The peak molecular
weight (MPeak or M.sub.P for short) in the GPC chromatogram
corresponds to the molar weight, according to calibration, at
maximum detector signal.
[0141] The polydispersity index from weighted (M.sub.w) and
number-average (M.sub.n) molecular weight from the gel permeation
chromatography is defined as M.sub.w/M.sub.n.
[0142] .sup.1H-NMR spectroscopy (proton resonance spectroscopy):
The measurements were performed using a Bruker AV400 instrument
(400 MHz); the chemical shifts were calibrated relative to the
solvent signal (CDCl.sub.3, .delta.=7.26 ppm); s=singlet,
m=multiplet, bs=broadened singlet, kb=complex region.
[0143] .sup.13C NMR spectroscopy: The measurements were performed
using a Bruker AV400 instrument (100 MHz); the chemical shifts were
calibrated relative to the solvent signal (CDCl.sub.3,
.delta.=77.16 ppm); HMBC: hetero multiple bond correlation.
[0144] The content of polyoxymethylene groups, polypropylene oxide
groups and polyethylene oxide groups in the polyol component was
determined using .sup.1H-NMR spectroscopy. The relative contents of
the individual increments were determined by integration of the
characteristic proton signals. These were also used for quantifying
conversions. Characteristic signals of the compounds produced
are:
[0145] .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.=1.14 (m, 3H,
methyl groups PO); 3.20-3.55 (m, 3H, ethylene groups PO); 3.73 (s,
4H, ethylene groups EO); 4.70-4.90 (m, 2H, methylene groups
formaldehyde FA) ppm.
[0146] .sup.13C NMR (75 MHz, CDCl.sub.3) .delta.=17.4 (methyl
groups PO); 66.9-67.5 (ethylene groups PO and EO); 75.5 (ethylene
groups PO); 73.0 (ethylene groups PO and EO); 88.0-95.5 (methylene
groups formaldehyde FA); 154.8 (carbonate) ppm.
Catalyst Synthesis
Synthesis of Catalyst C-1 Employable According to the Invention
[0147] To synthesize catalyst C-1 1.182 g of the
1,5-naphthalenedisulfonic acid disodium salt (3.556 mmol; 1.0 eq.)
were suspended in 15 ml of absolute dichloromethane under inert
conditions. With vigorous stirring, 0.19 ml of 98% sulfuric acid
(3.556 mmol; 1.0 eq.) were added. After 10 minutes of stirring the
solvent was removed under vacuum and the solid was dried under high
vacuum over 4 hours.
[0148] The obtained catalyst was used in further reactions without
further purification.
D=1.0
[0149] Alternatively, the catalyst C-1 may also be produced
directly in the presence of the starter (BH) in analogous fashion
with or without dichloromethane.
Synthesis of Catalyst C-2 Employable According to the Invention
[0150] To synthesize catalyst C-2 3.709 g of the
1,3-benzenedisulfonic acid disodium salt (13.158 mmol; 1.0 eq.)
were suspended in 30 ml of absolute dichloromethane under inert
conditions. With vigorous stirring, 0.70 ml of 98% sulfuric acid
(13.158 mmol; 1.0 eq.) were added. After 10 minutes of stirring the
solvent was removed under vacuum and the solid was dried under high
vacuum over 4 hours.
[0151] The obtained catalyst was used in further reactions without
further purification.
D=1.0
[0152] Alternatively, the catalyst C-2 may also be produced
directly in the presence of the starter (BH) in analogous fashion
with or without dichloromethane.
Synthesis of Catalyst C-3 Employable According to the Invention
[0153] To synthesize catalyst C-3 2.000 g of the
1,5-naphthalenedisulfonic acid disodium salt (6.019 mmol; 1.0 eq.)
were suspended in 15 ml of absolute dichloromethane under inert
conditions. With vigorous stirring, 0.898 ml of
trifluoromethanesulfonic acid (1.535 g; 10.233 mmol; 1.7 eq.) were
added. After stirring for 10 minutes the solvent was removed under
vacuum.
[0154] The obtained catalyst C-3 was used in further reactions
without further purification.
D=1.7
[0155] Alternatively, the catalyst C-3 may also be produced
directly in the presence of the starter (BH) in analogous fashion
with or without dichloromethane.
Synthesis of Catalyst C-4 Employable According to the Invention
[0156] Analogously to the preparation of catalyst C-3 the catalyst
C-4 was produced with a degree of protonation D of D=1.3. The
amount of the trifluoromethanesulfonic acid was employed according
to the degree of protonation D=1.3.
D=1.3
[0157] Alternatively, the catalyst C-4 may also be produced
directly in the presence of the starter (BH) in analogous fashion
with or without dichloromethane.
Synthesis of Catalyst C-5 Employable According to the Invention
[0158] 1.171 g (3.525 mmol) of 2,6-naphthalenedisulfonic acid
disodium salt were suspended in absolute dichloromethane and
admixed with 0.41 ml (4.700 mmol; 0.705 g) of
trifluoromethanesulfonic acid. The suspension was stirred over 20
minutes and subsequently concentrated under vacuum.
[0159] The obtained catalyst C-5 was used in further reactions
without further purification.
D=1.3
[0160] Alternatively, the catalyst C-5 may also be produced
directly in the presence of the starter (BH) in analogous fashion
with or without dichloromethane.
Synthesis of Catalyst C-6 Employable According to the Invention
[0161] Analogously to the preparation of catalyst C-5 the catalyst
C-6 was produced with a degree of protonation D of D=1.7. The
amount of the trifluoromethanesulfonic acid was employed according
to the degree of protonation D=1.7.
D=1.7
[0162] Alternatively, the catalyst C-6 may also be produced
directly in the presence of the starter (BH) in analogous fashion
with or without dichloromethane.
Synthesis of Catalyst C-7 Employable According to the Invention
[0163] To synthesize catalyst C-7 32 mg of fumaric acid (0.280
mmol; 1 eq) were dissolved in 0.47 ml of a solution of
tetrabutylammonium methoxide (0.280 mmol; 20% in methanol; 1 eq).
The obtained mixture was then concentrated to dryness.
[0164] The obtained catalyst C-7 was used in further reactions
without further purification.
D=1.0
Synthesis of Catalyst C-8 Employable According to the Invention
[0165] Analogously to the preparation of catalyst C-7 the catalyst
C-8 was produced, 1,5-naphthalenedisulfonic acid being employed as
the diprotic acid instead of fumaric acid. The degree of
protonation of the resulting catalyst C-8 is D=1.0.
TABLE-US-00001 TABLE 1 Production of the organic, n-protic Bronsted
acid (C) as catalyst Step .alpha. Step .beta. organic, salt of the
n-protic organic, Bronsted n-protic Catalyst acid base (EH)
Bronsted acid Acid (E') D n C-1 1,5-Na2-NDS H2SO4 1.0 2 C-2
1,3-Na2-BDS H2SO4 1.0 2 C-3 1,5-Na2-NDS CF3SO3H 1.7 2 C-4
1,5-Na2-NDS CF3SO3H 1.3 2 C-5 2,6-Na2-NDS CF3SO3H 1.3 2 C-6
2,6-Na2-NDS CF3SO3H 1.7 2 C-7 Fumaric acid (n-Bu).sub.4N 1.0 2
(OMe) C-8 1,5-NDS (n-Bu).sub.4N 1.0 2 (OMe)
Activity Tests
Example 1: Reaction of Styrene Oxide with pFA in the Presence of
Catalyst C-1
[0166] In an inertized Schlenk flask with a magnetic stirrer 12.0 g
of finely powdered paraformaldehyde (pFA, M=450 g/mol; 27.500 mmol;
1.00 eq) were suspended in 25 ml of absolute 1,3-dioxolane. The
batch was heated to 50.degree. C. and 119 mg of the catalyst C-1
were added with stirring (0.275 mmol; 0.01 eq). Over a period of 72
hours 38 ml of styrene oxide (330.000 mmol; 12 eq) were added
dropwise to form a stable white solution. The reaction was
monitored by NMR. To this end the crude product was dissolved in
dichloromethane, separated from undissolved constituents by
filtration and concentrated under vacuum.
[0167] The conversion of styrene oxide was 100%.
[0168] The number-average molecular weight M.sub.n was 1300 g/mol.
The molecular weight distribution determined by GPC was
monomodal.
[0169] The polydispersity index was 1.99.
Example 2: Reaction of Styrene Oxide with pFA in the Presence of
Catalyst C-1
[0170] In an inertized Schlenk flask with a magnetic stirrer 44.0 g
of finely powdered pFA (M=450 g/mol; 110.000 mmol; 1.00 eq) were
suspended in 25 ml of absolute 1,3-dioxolane. The batch was heated
to 50.degree. C. and 474 mg of the catalyst C-1 were added with
stirring (1.100 mmol; 0.01 eq). Over a period of 48 hours 151 ml of
styrene oxide (132.000 mmol; 12 eq) were added dropwise to form a
stable white solution. The reaction was monitored by NMR. To this
end the crude product was dissolved in dichloromethane, separated
from undissolved constituents by filtration and concentrated under
vacuum.
[0171] The conversion of styrene oxide was 100%.
[0172] The number-average molecular weight M.sub.n was 1758
g/mol.
[0173] The molecular weight distribution determined by GPC was
monomodal.
[0174] The polydispersity index was 1.90.
Example 3: (Comparative Example) Reaction of Styrene Oxide with PEG
in the Presence of Sodium Hydrogensulfate as Catalyst
[0175] In an inertized Schlenk flask with a magnetic stirrer 550 mg
of PEG (M=1000 g/mol; 0.550 mmol; 1.00 eq) were heated to
50.degree. C. and 1 mg of sodium hydrogensulfate (0.006 mmol; 0.01
eq) were added with stirring. Subsequently 0.52 ml of styrene oxide
were added (4.400 mmol; 8.00 eq) and the reaction mixture was
heated to 50.degree. C. over three hours.
[0176] The reaction product was analyzed by NMR spectroscopy
without further purification.
[0177] No conversion of the employed styrene oxide was
observed.
Example 4: Reaction of Propylene Oxide with PEG in the Presence of
Catalyst C-5
[0178] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt
(0.021 mmol, 0.015 eq) were mixed with 1375 mg of PEG (M=1000
g/mol; 1.375 mmol; 1.00 eq) in an oven-dried pressure-resistant
reaction vial. 4 mg of trifluoromethanesulfonic acid (0.028 mmol,
0.02 eq) were added and the mixture was thoroughly commixed at
60.degree. C. At room temperature 0.77 ml of propylene oxide
(11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed
and the contents were stirred at a temperature of 60.degree. C.
over 1.5 hours.
[0179] Further analysis was performed without workup of the
reaction mixture.
[0180] The conversion of propylene oxide was 100%.
[0181] M.sub.n of the product was 1343 g/mol.
Example 5: Reaction of Propylene Oxide with pFA in the Presence of
Catalyst C-4
[0182] 7.5 mg of 1,5-naphthalenedisulfonic acid disodium salt
(0.021 mmol; 0.015 eq) were mixed with 550 mg of finely powdered
pFA (M=450 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried
pressure-resistant reaction vial. 4 mg of trifluoromethanesulfonic
acid (0.028 mmol; 0.02 eq) were added and the mixture was
thoroughly commixed. From a total amount of 0.77 ml of propylene
oxide (11.000 mmol; 8.0 eq) 0.3 ml were added and the mixture was
thoroughly stirred. The addition of propylene oxide was
subsequently completed, the reaction vessel was sealed and the
mixture was stirred at a temperature of 70.degree. C. over six
hours.
[0183] Further analysis was performed without workup of the
reaction mixture.
[0184] The conversion of propylene oxide was 100%.
[0185] M.sub.n of the product was 730 g/mol.
Example 6: Reaction of Propylene Oxide with pFA in the Presence of
Catalyst C-5
[0186] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt
(0.021 mmol; 0.015 eq) were mixed with 550 mg of finely powdered
pFA (M=450 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried
pressure-resistant reaction vial. 4 mg of trifluoromethanesulfonic
acid (0.028 mmol; 0.02 eq) were added and the mixture was
thoroughly commixed. From a total amount of 0.77 ml of propylene
oxide (11.000 mmol; 8.0 eq) 0.3 ml were added and the mixture was
thoroughly stirred. The addition of propylene oxide was
subsequently completed, the reaction vessel was sealed and the
mixture was stirred at a temperature of 70.degree. C. over six
hours.
[0187] Further analysis was performed without workup of the
reaction mixture.
[0188] The conversion of propylene oxide was 100%.
[0189] M.sub.n of the product was 738 g/mol.
Example 7: Reaction of Allyl Glycidyl Ether with PEG in the
Presence of Catalyst C-6
[0190] Under inert gas 2.4 mg of the catalyst 6 (0.004 mmol; 0.8
mol %) were mixed with 500 mg of PEG (M=1000 g/mol; 0.500 mmol;
1.00 eq) in an oven-dried Schlenk tube. At room temperature 0.24 ml
of allyl glycidyl ether (2.000 mmol; 4.0 eq) were added, the
reaction vessel was sealed and the contents were stirred at a
temperature of 60.degree. C. over 8 hours.
[0191] Further analysis was performed without workup of the
reaction mixture.
[0192] The conversion of allyl glycidyl ether was 82%.
[0193] The number-average molecular weight M.sub.n was 1634
g/mol.
[0194] The molecular weight distribution determined by GPC was
monomodal in the polymeric range.
[0195] The polydispersity index was 1.8.
Example 8: Reaction of Ethylene Oxide with PET in the Presence of
Catalyst C-5
[0196] 1.171 g (3.525 mmol) of 2.6-naphthalenedisulfonic acid
disodium salt were suspended in absolute dichloromethane and
admixed with 0.41 ml (4.700 mmol; 0.705 g) of
trifluoromethanesulfonic acid. The suspension was stirred over 10
minutes and subsequently concentrated under vacuum. The obtained
white solid was then mixed with 10 g of PET (0.023 mol). The thus
obtained suspension was transferred into a 2 L high-pressure
reactor together with 91.5 g of PET (0.212 mol). The contents were
pressurized with nitrogen (1 bar) and subsequently evacuated in
three cycles to remove residual air. At a nitrogen pressure of 45
bar the reactor was heated to 45.degree. C. and stirred at 200 rpm.
Ethylene oxide 142.9 g (0.94 mol; 8 eq) was added at a rate of 2
ml/min and the reaction temperature was increased at 10.degree.
C./15 min until an internal temperature of 105.degree. C. had been
achieved (the exothermic reaction was observed above 90.degree.
C.). After cooling to 60.degree. C. the ethylene oxide
concentration in the gas phase was determined (below 5 ppm) and the
reactor was decompressed.
[0197] The conversion of ethylene oxide was 100%. The proportion of
secondary components was determined as 0.6% by weight.
[0198] The number-average molecular weight M.sub.n was 740
g/mol.
[0199] The molecular weight distribution determined by GPC was
monomodal in the entire range.
[0200] The polydispersity index was 1.2.
Example 9: Reaction of Ethylene Oxide with pFA in the Presence of
Catalyst C-5
[0201] 1.220 g (3.673 mmol) of 2,6-naphthalenedisulfonic acid
disodium salt were suspended in absolute dichloromethane and
admixed with 0.72 g (4.797 mmol) of trifluoromethanesulfonic acid.
The suspension was stirred over 10 minutes and subsequently
concentrated under vacuum. The obtained white solid was then mixed
with 108 g of cPC. The thus obtained suspension was transferred.
105.8 g of pFA (M=450 g/mol, 0.235 mol) were then added. The
contents were pressurized with nitrogen (1 bar) and subsequently
evacuated in three cycles to remove residual air. At a nitrogen
pressure of 45 bar the reactor was heated to 60.degree. C. and
stirred at 200 rpm. Ethylene oxide 142.8 g (0.94 mol, 8 eq) was
added at a rate of 2 ml/min and the reaction temperature was
increased at 10.degree. C./15 min until an internal temperature of
105.degree. C. had been achieved (the exothermic reaction was
observed above 90.degree. C.). After cooling to 60.degree. C. the
ethylene oxide concentration in the gas phase was determined (below
5 ppm) and the reactor was decompressed.
[0202] The conversion of ethylene oxide was 100%. The proportion of
secondary components was determined as 8.6% by weight.
[0203] The number-average molecular weight M.sub.n was 1409
g/mol.
[0204] The molecular weight distribution determined by GPC was
monomodal in the entire range.
[0205] The polydispersity index was 1.9.
Example 10: Reaction of 1,3-Dioxolane with pFA in the Presence of
Catalyst C-2
[0206] 12 g of finely powdered pFA (0.030 mol; 1.0 eq) were
suspended in 12 ml of absolute 1,3-dioxolane under inert
conditions. The mixture was heated to 65.degree. C. and the
catalyst 2 (342 mg; 0.009 mol; 0.03 eq) was added. The reaction
mixture was stirred over 7.5 hours. The product mixture was mixed
in 40 ml of dichloromethane, separated from undissolved
constituents by filtration and concentrated under vacuum.
[0207] Final weight: 10.2 g
[0208] The number-average molecular weight M.sub.n was 1953
g/mol.
[0209] The molecular weight distribution determined by GPC was
monomodal.
[0210] The polydispersity index was 1.8.
Example 11: Reaction of Propylene Oxide with PC in the Presence of
Catalyst C-5
[0211] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt
(0.021 mmol; 0.015 eq) were mixed with 4 mg of
trifluoromethanesulfonic acid (0.028 mmol; 0.02 eq) in an
oven-dried pressure-resistant reaction vial. 1375 mg of PC (M=1000
g/mol; 1.375 mmol; 1.00 eq) dissolved in 0.77 ml of propylene oxide
(11.000 mmol, 8.0 eq) were added and thoroughly stirred. The
reaction vessel was sealed and the mixture was stirred at a
temperature of 75.degree. C. over five hours.
[0212] Further analysis was performed without workup of the
reaction mixture.
[0213] Complete conversion of the employed propylene oxide with
negligible formation of cyclic propylene carbonate was observed.
Formation of new cyclic propylene carbonate was determined by
proton resonance spectroscopy and amounted to 2.7% of the
alternating polycarbonate groups.
[0214] The number-average molecular weight M.sub.n was 1381
g/mol.
[0215] The molecular weight distribution determined by GPC was
monomodal.
[0216] The polydispersity index was 1.3.
Example 12: (Comparative Example) Reaction of Propylene Oxide with
PC in the Presence of 1,8-diazabicyclo[5.4.0]Undec-7-Ene (DBU) as
Catalyst
[0217] 3 mg of 1,8-diazabicyclo[5.4.0]undec-7-ene (0.015 mmol;
0.015 eq) were initially charged in an oven-dried
pressure-resistant reaction vial. 1375 mg of PC (M=1000 g/mol;
1.375 mmol; 1.00 eq) dissolved in 0.77 ml of propylene oxide
(11.000 mmol, 8.0 eq) were added and thoroughly stirred. The
reaction vessel was sealed and the mixture was stirred at a
temperature of 75.degree. C. over five hours.
[0218] The reaction product was analyzed by NMR spectroscopy
without further purification.
[0219] Complete degradation of the polymer to cyclic propylene
carbonate was observed. No conversion of employed propylene oxide
into polymeric structures was observed.
Example 13: Reaction of Styrene Oxide with PEG in the Presence of
Catalyst C-7
[0220] 10 mg of catalystr C-7 tetrabutylammonium hydrogenfumarate
(0.028 mmol; 0.100 eq) were mixed with 275 mg of PEG (M=1000 g/mol;
0.275 mmol; 1.000 eq). The mixture was heated to 70.degree. C. and
0.13 ml of styrene oxide (1.100 mmol, 4.0 eq) were added. The batch
was stirred at 70.degree. C. over 10 hours.
[0221] The reaction product was analyzed by NMR spectroscopy
without further purification.
[0222] The conversion of employed styrene oxide was 28%.
[0223] An M.sub.n of 1135 g/mol was calculated from the NMR
analysis.
Example 14 (Comparative Example): Reaction of Propylene Oxide with
PEG in the Presence of Trifluoromethanesulfonic Acid as
Catalyst
[0224] Initially charged in an oven-dried pressure-resistant
reaction vial were 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00
eq). 4 mg of trifluoromethanesulfonic acid (CF.sub.3SO.sub.3H,
0.028 mmol, 0.02 eq) were added and the mixture was thoroughly
commixed at 60.degree. C. At room temperature 0.77 ml of propylene
oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was
sealed and the contents were stirred at a temperature of 60.degree.
C. over 1.5 hours.
[0225] Further analysis was performed without workup of the
reaction mixture.
[0226] The conversion of propylene oxide was 100%.
[0227] The molecular weight distribution determined by GPC was
multimodal in the polymeric range and exhibited a high proportion
of low molecular weight compounds. M.sub.n was 1292 g/mol.
Example 15 (Comparative Example): Reaction of Propylene Oxide with
PC in the Presence of Trifluoromethanesulfonic Acid as Catalyst
[0228] Initially charged in an oven-dried pressure-resistant
reaction vial were 4 mg of trifluoromethanesulfonic acid (0.028
mmol; 0.02 eq). 1375 mg of PC (M=1000 g/mol; 1.375 mmol; 1.00 eq)
dissolved in 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were
added and thoroughly stirred. The reaction vessel was sealed and
the mixture was stirred at a temperature of 75.degree. C. over five
hours.
[0229] Further analysis was performed without workup of the
reaction mixture.
[0230] Complete conversion of the employed propylene oxide with
severe formation of cyclic propylene carbonate was observed.
Formation of new cyclic propylene carbonate was determined by NMR
and amounted to 39% of the alternating polyethercarbonate
groups.
[0231] The number-average molecular weight M.sub.n was 808
g/mol.
[0232] The molecular weight distribution determined by GPC
exhibited high proportions of low molecular weight compounds.
[0233] The polydispersity index was 1.6.
Example 16 (Comparative Example): Reaction of Propylene Oxide with
pFA in the Presence of Trifluoromethanesulfonic Acid as
Catalyst
[0234] Initially charged in an oven-dried pressure-resistant
reaction vial were 550 mg of finely powdered pFA (M=450 g/mol;
1.375 mmol; 1.00 eq). 4 mg of trifluoromethanesulfonic acid (0.028
mmol; 0.02 eq) were added and the mixture was thoroug